TW305852B - - Google Patents

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TW305852B
TW305852B TW083110653A TW83110653A TW305852B TW 305852 B TW305852 B TW 305852B TW 083110653 A TW083110653 A TW 083110653A TW 83110653 A TW83110653 A TW 83110653A TW 305852 B TW305852 B TW 305852B
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acid
resin
adduct
unsaturated
patent application
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TW083110653A
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Chinese (zh)
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Ashland Inc
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06Unsaturated polyesters

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paper (AREA)

Description

Α7 Β7 1 五、發明説明( 發明背景 塑料物質之使用,例如供汽車外部零件用之以玻瑞纖維 增強之熱61㈣樹脂,呈穩定性增加。這些固化樹脂係由 於堅固、料、使形成單-料零件取代數個金屬零件成 爲可行而相當成功。然而’彼等較爲易碎,且基於消費者 對較佳品質之需求;其表面整理平滑㈣立鱧穩定性必須 改進。 有許多產品係用於改進塱料零件的表面品質,由於彼等 可減少表面粗糙性和改良表面平滑性或廓形"而稱之爲低 廓形添加劑(LPA’s)。當表面粗輪時,高倍率放大下之橫 截面顯示波峰和波谷。表面較平滑時,橫截面平滑些,具 有較低的波峰和較淺的波谷。有效的“▲會減少最高波峰 和最淺波谷間之差異。惟即使最佳的LPA也無法達成像鏡 面的表面。 含有聚丙二醇(PPG)、衆乙二醇(PEG)、ε -己内酯、和 PPG聚酯及二酸類之多種低聚物曾用於改進lpa,s之有效性 。然而,這些產品趙向導致固化樹脂系Barcol硬度和物理 性質類著的降低。片狀槔製化合物(SHC)以經基爲末端之 多醇和衆酯低衆物之使用所引起的其他問題包括打開模製 物時由於釋放的揮發物增加引起的"冒煙"。經調配和於使 用前貯存之系統,由於S旨基轉移作用的提昇及添加劑併入 綦底樹脂中,也可能遭受有效性之喪失〇若能鑑定出沒有 這些缺點而能改進低廓形添加劑的效能並提供較佳的A" 級表面之物質則較爲有利。 本紙張尺度適用中國國家橾準(CNS ) Μ规格(21〇><297公釐〉 (請先Μ讀背面之注意事項再填寫本頁)Α7 Β7 1 V. Description of the invention (The use of plastic materials, such as heat 61㈣ resin reinforced with Borui fibers for automotive exterior parts, shows an increase in stability. These cured resins are formed due to the strength, material, and form of single- The replacement of several metal parts by material parts has become feasible and quite successful. However, they are more fragile and based on consumers' demand for better quality; their surface finishing is smooth and the stability of the standing snake must be improved. There are many products used In order to improve the surface quality of the material parts, they can be called low profile additives (LPA's) because they can reduce surface roughness and improve surface smoothness or profile. When the surface is rough, high magnification magnifies it. The cross-section shows peaks and troughs. When the surface is smoother, the cross-section is smoother, with lower peaks and shallower troughs. Effective "▲ will reduce the difference between the highest peaks and the shallowest troughs. But even the best LPA It is also impossible to reach the surface of the imaging mirror. Contains polypropylene glycol (PPG), ethylene glycol (PEG), epsilon-caprolactone, and PPG polyester and diacids of various oligomers used In order to improve the effectiveness of lpa, s. However, these products Zhao Xiang led to a similar reduction in the hardness and physical properties of the cured resin system Barcol. Tablet-like compound (SHC) with polyols and esters as the end of the warp group Other problems caused by the use of the product include " smoke " caused by the increase in volatiles released when the molded product is opened. The system that has been formulated and stored before use, due to the enhancement of the S-base transfer effect and the incorporation of additives The bottom resin may also suffer from a loss of effectiveness. It is more advantageous to identify substances that can improve the performance of low profile additives and provide better A " grade surfaces without these shortcomings. This paper size is suitable for China National Standard (CNS) M specifications (21〇 < 297mm> (Please read the precautions on the back before filling this page)

,tT 經濟部中央橾準局員工消f合作社印製 經濟部中夫橾隼局員工消費合作杜印製, tT Printed by the Ministry of Economic Affairs, Central Bureau of Precincts, Employee Consumer Cooperatives, printed by the Ministry of Economic Affairs

Su5652 A7 B7 ' 1 ' -.「 -.-- — 五、發明説明(2 ) 以脂肪酸例如硬脂酸、月桂酸和高油封端(capped)之多 醇和衆酯低聚物被發現比未封端之低衆物更爲有效。以脂 肪酸封端之物質也證實爲極佳之濕揭劑,提供改良之固體 分散性、黏度和流動性。以脂肪酸封端之低聚物也改進模 製零件之釋放性(release)和表面先澤。出乎意外地,封 端似乎減少了在模製SMC時有時見到的"冒*煙",且顯著地 減少醏基轉移作用’因此延長添加劑在調釔後貯存的系統 中之有效性。 在固化樹脂中可相容的某些低廓形添加劑改進劑被發現 對Barcol硬度和物理性質有顯著的負面影響,同時也似乎 阻礙低恩模製化合物(LPMC)之固化。低壓模製化合物係以 結晶型不飽和基底樹脂、低靡形添加劑和反應性不飽和單 體,以及抑制劑,固化引發劑與填充劑調配成的。此LPMC 調配物在120*F以上爲液體,但冷卻到9〇«p以下時,基底 樹脂結晶化、調配物固化,達到超過5千萬厘泊的黏度。 LPMC薄片之製備和片狀模製化合物相同,惟僅含足夠的玻 瑞以供處理(2-6重量百分比)。於約9〇.c(i94°F )將薄片切 片置於轉模中的玻璃纖維預成形上❶鏵模閉合時,結晶型 樹脂熔融,在很低的壓力下,成爲液體的樹脂流動並充滿 鑄模腔,於5至10分鐘内即固化成成品零件。 固化熱固性基質之數據顯示LPMC物理性質之負面效果係 申可溶性添加刺對基質的增塑性所引起。根據推理,與固 化基質不相容的添加劑即不具此等增塑效果而產生較佳的 物理性質,因而鐘明其他低衆物,在以各種脂肪酸封端後 本紙張疋度適用中國國家標準(CNS ) Ad規格(210χ297公釐) m Hi m I— ml I ii I-----0 I Ϊ n^— - - 1 - (請先閱讀背面之注意事項再填寫本f)Su5652 A7 B7 '1'-. "-.---V. Description of the invention (2) Polyols and oligomers capped with fatty acids such as stearic acid, lauric acid and high oil capped were found to be unsealed The low-end products are more effective. The fatty acid-terminated materials have also proven to be excellent wet-release agents, providing improved solid dispersion, viscosity and fluidity. The fatty acid-terminated oligomers also improve molded parts The release and surface appearance. Unexpectedly, the end-blocking seems to reduce the "quote" smoke sometimes seen when molding the SMC, and significantly reduces the effect of acetyl radical transfer. The effectiveness of the additives in the storage system after yttrium adjustment. Certain low profile additive improvers that are compatible in cured resins have been found to have a significant negative impact on Barcol hardness and physical properties, and also seem to hinder low enmole LPMC curing. Low-pressure molding compounds are formulated with crystalline unsaturated base resins, low-volume additives and reactive unsaturated monomers, as well as inhibitors, curing initiators and fillers. This LPMC formulation Within 120 * F It is a liquid, but when it is cooled below 90 ° p, the base resin crystallizes and the formulation solidifies, reaching a viscosity of more than 50 million centipoise. The preparation of LPMC flakes is the same as that of sheet molding compounds, but only contains enough glass For processing (2-6 weight percent). Place the thin slices on the glass fiber preform in the rotary mold at about 9〇.c (i94 ° F). ❶ When the mold is closed, the crystalline resin melts, Under low pressure, the resin that becomes a liquid flows and fills the mold cavity and solidifies into a finished part within 5 to 10 minutes. The data of the cured thermosetting matrix shows that the negative effect of the physical properties of LPMC is due to the plasticity of the matrix added by soluble soluble thorns. According to the reasoning, additives that are incompatible with the cured matrix do not have such plasticizing effects and produce better physical properties, so Zhong Ming other low-grade objects, after being capped with various fatty acids, this paper is suitable for China. Standard (CNS) Ad specifications (210 × 297 mm) m Hi m I— ml I ii I ----- 0 I Ϊ n ^ —--1-(please read the precautions on the back before filling in this f)

專利申請案第83110653號 ROC Patent Appln. No.83110653 _ :炎丨 中义説明書修正頁-附件(三)Patent Application No. 83110653 ROC Patent Appln. No. 83110653 _: Yan 丨 Zhongyi Specification Revision Page-Annex (3)

Amended Pages oP^the Chinese Specification - Enel 二 (氏國84牛Ίυ片今〇 d~~修主並送呈厂^ 五、發明说明(S ) (Amended & Submitted on October ->c? ; 1995) ,於固化期間在基質内形成分離相。這些以脂肪酸封端之 低I物成加合物與固化不飽和聚錯及單體不相容而爲低靡 形添加刻。評估顯示多數多封端低聚物爲有效之表面品 質故進劍,於固化熱固定中不相容’且典型地對物理性質 和Barcol硬度顯示很小的負面影響。 頃發現與固化熱固性基質不相容、有沒低廓形添加劑故 進之多封端低聚物,可由以脂肪酸封端之多種低衆物予以 製備。由於這些化合物在固化期間形成分離相’使其對物 理性質和Barcol硬度之負面影響大爲減少。此外,此等添 加劑爲有效的濕潤劑,可減少填充樹脂之處理黏度及增進 填充劑分散性、流動性、表面光澤和镑模釋放性。 ®式說明 圖1爲根據美國專利4,853,777所述數値指數之模製板 ! 片表面品質之圖形。指數値愈低’表面愈佳或愈平滑。鋼 板的指數爲70-90,玻璃板的指數爲15_25。模製複合材料 外部車體面板應具有50-70之指數。含有不飽和衆能樹脂 、.低靡形添加劑、反應性單體和多封端低聚物故進劑的三 個模製調配物之低廓形添加劑和改進刻的濃度以每百份樹 脂之份數示之。圖形係記綠於零份本發明改進劑(圓圈)、 一份本發明之多封端低聚物改進劑(三角形)、及四份本發 明之多封端低聚物故進刻(正方形).存在下’各種低.靡形添 >劑含量之表面品質。 發明‘之詳細説明 本發明係使用於聚δ旨熱固模製組成物之固化基質中不相 訂 ^ 1·^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作社印製 本紙張尺度適用中國國家標準(〇^)八4祕(21〇><297公釐)Amended Pages oP ^ the Chinese Specification-Enel II (84 NIU Ίυ tablets of the country's 84 ~~ repaired and submitted to the factory ^ V. Invention description (S) (Amended & Submitted on October-> c ?; 1995) , Forming a separate phase in the matrix during curing. These fatty acid-terminated low-I adducts are incompatible with the cured unsaturated polyimide and monomers and are added to the low profile. Evaluation shows that most multi-terminated low Polymers are effective surface qualities, so they are incompatible, and are incompatible in curing heat fixation and typically show very little negative impact on physical properties and Barcol hardness. It is found that they are incompatible with cured thermosetting matrices and have low profile The multi-terminated oligomers that are used in the form of additives can be prepared from a variety of low-end materials terminated with fatty acids. Because these compounds form a separate phase during curing, their negative effects on physical properties and Barcol hardness are greatly reduced. In addition, these additives are effective wetting agents, which can reduce the processing viscosity of the filled resin and improve the filler's dispersibility, fluidity, surface gloss and mold release. ® Formula Description Figure 1 is based on the United States The molded board with the numerical value index mentioned in 4,853,777! The graphic of the surface quality of the sheet. The lower the index value, the better or smoother the surface. The index of the steel plate is 70-90, and the index of the glass plate is 15_25. The exterior body panel of the material should have an index of 50-70. Low profile additives containing three molded formulations containing unsaturated versatile resin, low profile additives, reactive monomers and multi-block oligomers The concentration of the modified engraving is shown in parts per hundred parts of resin. The graph is marked in green with zero parts of the modifier of the invention (circle), a part of the multi-blocked oligomer modifier of the invention (triangle), and four The multi-capped oligomer of the present invention is engraved (square). In the presence of the surface quality of the "various low. Meso-modified> agent content. Detailed description of the invention" The present invention is used in poly delta thermosetting molding The curing matrix of the composition does not match ^ 1 · ^ (Please read the precautions on the back before filling in this page) The paper standard printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs is applicable to the Chinese National Standard (〇 ^) 8 4 secret (21〇 < 297mm)

A B 修丨 305852 補充^ 五、發明説明(+ ) 容的多封端低蒎物改進劑,改進低廓形添知劑的效能及吹 進此等模製組成物的收缩控制和表面品質之用途。此等多 封端低象物玖進劑係以對酞酸、異鈦酸及其他二羧酸織鸟 基底,與乙二醇類例如乙二醇、二乙二醇' 1,4-丁二鮮反 應,並以具有八至十二個碳原子之脂肪酸例如高油脂肪_酸 、月桂酸、硬脂酸或油酸封端之低分子董蒗酯低聚物。 此等封端低聚物單獨使用時並不是有效的低廓形添知飼 ,惟類著地增加典型低廓形添加劑之效能。由於彼等於固 化熱固基質中不溶(不相容),且於固化反應期間形成分離 相,因此在相容添加劑將固化熱固基質増.塑中典型可見的 物理性質和Barco 1硬度之喪失即顯著地減少或消除。腸&amp; 酸末端基團也使此添加劑成爲非常有效的濕潤劑,減少處 理黏度及增進固體分散性、光澤、鑄模釋放性、和樹脂&amp; 動性。對模製物之評估也顯示,以多封端低聚物改進劑取 :代一部分低廓形添加劑得到相等或較佳之表面品質,同時 ,物理性質例如抗張強度和抗彎強度也頡著增加。這告故 進劑也降低固化零件對水之吸收性。 參照圖1,其明顯地示出一或四份改進劑對SMC中胺隨 交聯衆酯多醇低廓形添加劑的影響。不含改進劑(圓圈)之 曲線圖數據顯示,於16phr低廓形添加劑處,得到大約75 之最佳表面品質。加一扮改進劑將表面品質從約75增進到 65,而加四份改進劑進一步地將表面品質增造至約55(單 箭)。 對圖1中對角破折線之研究透露本發明之實際應用。此 —6. 本紙張又度逋用中國國家梂準(CNS ) A4規格(21〇χ297公釐) __________裝------·'訂------^ ^ 〈琦先閲讀背面之注意事項再填寫本頁) __ 經濟部中央橾準局員工消费合作社印製 經濟部中央標準局貝工消費合作社印製 A7 B7 五、發明説明(5) 顯示使用者利用加入1份多封端低聚物改進劑可將低廓形 添加劑從16份減少至14份而達到增進之表面品質68,且增 加物理特性,例如抗張強度。同樣地,較佳之表面品質組 合和增進之物理性可利用將低廓形添加劑降至12份及加入 4份改進劑而獲得,所得表面品質爲60,抗張強度有所增 進。 . 本發明所用多封端低聚物之聚醏樹脂系的第一個成分爲 不飽和聚醏樹脂。其典型的製法爲將不飽和酸或酸酑與多 元酵反應,利用熟悉聚酯技術者悉知之方法和反應物。參 考,例如,Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 18,pages 575-580 (1982),整個揭示内容併入本文以資參考。典型反應物包 括順丁烯二酸、反丁烯二酸、烏頭酸、甲基反丁烯二酸、 順丁烯二酐、分解烏頭酑、甲基順丁烯二酑、其混合物及 類似物,和乙二醇類,例如乙二醇、二乙二酵、三乙二醇 、聚乙二醇、丙二醇、二丙二醇、聚丙二醇、1,3-丁二醇 、1,4-丁二醇、新戊基乙二醇、環己垸二甲醇、2,2,4-三 甲基戍二醇、乙氧基化及/或丙氧基化雙酚A、三揮甲基 乙垸、氩化雙酚A、三租甲基丙烷、二環戊二烯乙二酵、 二溴新戊基乙二酵、其混合物及類似物◊在某些情形下, 聚醏樹脂可進一步地含有,成爲共縮合單位,之其他化合 护,例如作爲改良劑用之二元芳族酸和酸酑及飽和脂族二 元酸。此等化合物之實例包括酞酸酑、異酞酸、己二酸、 琥难酸、壬二酸、癸二酸等以及對gi酸、各種氫化酞酸酐 -7- 本紙張尺度適用中國國家榡隼(CMS ) A4規格(210X297公釐) ---------------ir------Λ. (請先閲讀背面之注意事項再填寫本頁) 經濟部中央橾準局員工消費合作社印装 A7 B7 五、發明説明(6) 衍生物、偏苯三酸酑、環己烷二羧酸、氣菌酸、四溴S太酸 及四氣酞酸之酸时等。非晶型和晶型不飽和聚合物樹脂及 其混合物均可與本發明之多封端低衆物改進劑一起使用。 本發明所用多封端低衆物之樹脂組成物的第二個成分爲 增進模製用品表面品質之熱塑性添加劑,一般稱之爲低廓 形添加劑(LPAs)。有一此等添加劑爲得自_Ashland Chemical Company, Division of Ashland Oil, Inc.之 URALLOY雜化衆合物低廓形添加劑,美國專利4,421,894( 該文獻併入本文以資參考)中所述之異氰酸酯-端基預聚物 與聚酯多元酵之聚胺酯低聚物反應產物。與本發明添加劑 同樣有用之其他低廓形添加劑包括聚醋酸乙烯酯聚合物和 共聚物、衆丙烯酸醏、衆甲基丙烯酸酯,和共衆物例如衆 甲基丙烯酸曱S旨、衆丙歸酸曱醋、聚丙烯酸丁 8旨,及以二 元酸或酸酑例如琥珀酸、己二酸、癸二酸、St酸、異S太酸 、對酞酸、偏苯三酸酑等,與乙二醇類例如乙二醇、二乙 二醇、丙二醇、二丙二醇、新戊基乙二醇、衆環氧乙垸之 乙二醇、聚環氧丙烷之乙二轉、丁二酵、環己烷二甲醇等 。同時也‘括各種苯乙烯聚合物和共來物例如衆苯乙烯-丁二烯等。 樹脂组成物之第三成分爲本發明之多封端低聚物。多封 端低聚物之製備係將多官能低衆物與2或多個脂肪酸反應 •。可使用的多官能低聚物之實例包括下列諸式之多元酵類: 本紙张尺度適用中國國家橾牟(CNS ) A4C格(210X297公釐) 装 訂.^ (請先閱讀背面之注意事項再填寫本頁) 3u5S52 A7 _ B7 五、發明説明(7 )AB 修 丨 305852 Supplement ^ V. Description of the invention (+) The multi-block low pin content improver to improve the performance of low profile additives and the application of shrinkage control and surface quality of these molded compositions . These multi-capped low-elephant admixtures are based on terephthalic acid, isotitanic acid and other dicarboxylic acid weaving bird substrates, and glycols such as ethylene glycol, diethylene glycol '1,4-butanediol Fresh reaction, and low molecular weight donglin ester oligomers terminated with fatty acids having 8 to 12 carbon atoms, such as high oil fat acid, lauric acid, stearic acid or oleic acid. These end-capped oligomers are not effective low profile additives when used alone, but only significantly increase the effectiveness of typical low profile additives. Since they are insoluble (incompatible) in the cured thermosetting matrix and form separate phases during the curing reaction, the compatible additives will cure the thermosetting matrix. The physical properties typically seen in plastics and the loss of Barco 1 hardness are Significantly reduce or eliminate. Intestinal &amp; acid end groups also make this additive a very effective wetting agent, reducing processing viscosity and improving solid dispersibility, gloss, mold release, and resin &amp; motility. The evaluation of the molded product also shows that the multi-blocked oligomer modifier is used to substitute a part of the low-profile additive to obtain equal or better surface quality, and at the same time, the physical properties such as tensile strength and flexural strength are also increased . This also leads to a reduction in the absorption of water by the cured parts. Referring to Fig. 1, it clearly shows the effect of one or four parts of the modifier on the low profile additive of the amine in the SMC with the cross-linked urethane polyol. The graph data without the improver (circle) shows that at 16 phr low profile additives, the best surface quality of about 75 is obtained. Adding a modifier improves the surface quality from about 75 to 65, and adding four modifiers further increases the surface quality to about 55 (single arrow). The study of the diagonal dashed line in Figure 1 reveals the practical application of the present invention. This—6. This paper also uses the Chinese National Standard (CNS) A4 specification (21〇χ297 mm) __________ installed ------ · 'ordered ------ ^ ^ <Qi first read (Notes on the back and then fill out this page) __ Printed by the Ministry of Economy Central Bureau of Accreditation Employee Consumer Cooperative Printed by the Ministry of Economic Affairs Central Standards Bureau Beigong Consumer Cooperative Printed A7 B7 V. Description of invention (5) Show users to use to add more than one seal The terminal oligomer improver can reduce the low profile additive from 16 parts to 14 parts to achieve an improved surface quality of 68, and increase physical properties, such as tensile strength. Similarly, a better combination of surface quality and improved physical properties can be obtained by reducing the low profile additive to 12 parts and adding 4 parts of improver. The resulting surface quality is 60 and the tensile strength has increased. . The first component of the polyresin resin system of the multi-capped oligomer used in the present invention is an unsaturated polyresin resin. The typical preparation method is to react unsaturated acid or acid nitrate with polyaccharase, using methods and reactants known to those skilled in polyester technology. With reference to, for example, Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 18, pages 575-580 (1982), the entire disclosure is incorporated herein by reference. Typical reactants include maleic acid, fumaric acid, aconitic acid, methyl fumaric acid, maleic dianhydride, decomposed aconite, methyl maleic dioxin, mixtures thereof and the like , And glycols, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol , Neopentyl glycol, cyclohexane dimethanol, 2,2,4-trimethylpentanediol, ethoxylated and / or propoxylated bisphenol A, trifluoromethyl ethane, argon Bisphenol A, tri-l-propanepropane, dicyclopentadiene glyphosate, dibromo neopentyl glyphosate, mixtures and the like ◊ In some cases, the poly (resin) resin may be further contained and become Co-condensation units, other compound protection, such as binary aromatic acids and acids used as modifiers and saturated aliphatic dibasic acids. Examples of such compounds include phthalic acid fumarate, isophthalic acid, adipic acid, succinic acid, azelaic acid, sebacic acid, etc., as well as p-giic acid and various hydrogenated phthalic anhydride-7- This paper scale is applicable to the Chinese national falcon (CMS) A4 specification (210X297mm) --------------- ir ------ Λ. (Please read the precautions on the back before filling this page) Central Ministry of Economic Affairs Printed on the A7 B7 by the Consumers ’Cooperative of the Prospective Bureau V. Description of the invention (6) Derivatives, acid of trimellitic acid, cyclohexanedicarboxylic acid, aerobic acid, tetrabromo S too acid and tetragas phthalic acid Wait. Both amorphous and crystalline unsaturated polymer resins and mixtures thereof can be used with the multi-end low profile modifier of the present invention. The second component of the multi-capped low-profile resin composition used in the present invention is a thermoplastic additive for improving the surface quality of molded articles, generally referred to as low profile additives (LPAs). One such additive is the isocyanate described in URALLOY Hybrid Low Profile Additives from Ashland Chemical Company, Division of Ashland Oil, Inc., U.S. Patent 4,421,894 (which is incorporated herein by reference) The reaction product of terminal prepolymer and polyester oligoester oligomer. Other low profile additives that are equally useful as the additives of the present invention include polyvinyl acetate polymers and copolymers, methacrylates, methacrylates, and common substances such as methacrylate, methacrylate, and propionic acid Vinegar, polyacrylic acid butadiene, and dibasic acids or acids such as succinic acid, adipic acid, sebacic acid, St acid, iso-succinic acid, terephthalic acid, trimellitic acid, etc. Glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, ethylene glycol of ethylene oxide, ethylene oxide conversion of polypropylene oxide, succinase, cyclohexane Alkane dimethanol, etc. It also includes various styrene polymers and conjugates such as styrene-butadiene, etc. The third component of the resin composition is the polycapped oligomer of the present invention. The preparation of multi-capped oligomers is the reaction of multi-functional conglomerates with 2 or more fatty acids. Examples of polyfunctional oligomers that can be used include the following types of multi-enzymes: This paper size is suitable for China National Moumou (CNS) A4C format (210X297mm) binding. ^ (Please read the precautions on the back first (Fill in this page) 3u5S52 A7 _ B7 5. Description of the invention (7)

-(R-KC-. C— 0H)X (HOi-R-O)tC I i y-(R-KC-. C— 0H) X (HOi-R-O) tC I i y

R R I 或 K . 式中X^2 式中R基困可爲氫或烷基,R,爲雙酚A之環氧乙垸及/或 環氧丙垸加合物、酚醛樹脂之環氧乙烷及/或環氧丙垸加 合物、和纖維素製品及/或其環氧乙烷或或環氧丙燒加合 物。結構II之低聚物也可作爲這些添加劑之多元醇部份用 ,其中R可爲垸基、環垸基、或芳基及G爲多官能基團( yg 2),其可含有垸基、芳基、醚、多醚、酯、多醏、胺 醏或聚胺酯諸鍵。同時有用的爲類似之多官能環氧化物’ 其形成多封端低聚物係由環氧化物和酸利用親核加成反應 得到厶m酯類。此外,各種醇酸樹脂於本發明中也有用。 醉酸掛脂爲本項技藝中所悉知,參考例如Kirk-Othmer, 3rd edition, vol. 2,p.18。通常此等低衆物之平均分子 量很低,較佳爲2000以下。低聚物典型地爲鉋和化合物’ .... · · · 經濟部中央標準局員工消費合作社印裝 然而只要其特定之不飽和部份對苯乙烯之反應性低,則其 某些程度之不飽和是被容許的。低衆物之二或多個官能位 事易於輿具有8至22個碳原子之長鏈脂肪酸相連接。 與多官能低聚物反應的有用之C8至C22單官能酸包括: 月桂酸、亞麻油酸、次亞麻油酸、油硬脂酸、硬脂酸、篦麻油 酸、十一酸、十七酸、crucic acid、標櫚油酸、反油酸、辛 —9- 本紙張尺度適用中國國家榡率(CNS ) A4規格(210X297公釐) 經濟部中央標準局員工消費合作社印裝 A7 B7 五、發明説明(8 ) 酸、2-乙基己酸、壬酸、癸酸、油酸、肉笪蔻酸、棕搁酸 、花生酸、二十二酸、斑鳩萄酸、高油脂肪酸、及其混合 物。月桂酸、硬脂酸、及高油脂肪酸爲較佳之酸。 樹脂系之第四成分爲輿不飽和聚醏成分共衆合之一或多 個烯烴不抱和單體。有用的單體包括苯乙烯、甲基丙烯酸 甲醋、二乙烯苯、〇(-甲基苯乙烯、醋酸乙烯醏、各種垸 基丙烯酸醏和烷基甲基丙烯酸醏等。最常用和最佳之單髏 爲笨乙稀。 附加之視需要成分包括鱗模釋放劑例如硬脂酸辞和硬脂 酸鈣,填充劑例如碳酸鈣、飄塵、木粉、雲母、玻璃珠或 陶瓷珠、固化加速劑例如有機鈷化合物、固化引發劑例如 過氧化醋、二烷基過氧化物、烷基芳基過氧化物、二芳基 過氧化物、過氧化缩酮和酮過氧化物。抑制劑例如丁基經 基甲笨(BHT)、對苯醌(PBQ)、氫联(HQ)、四氫醌(THQ), 也爲視需要之成分。此外,有些樸製组成物例如片狀模製 化合物(SMC)或塊狀模製化合物(BMC)在將玻璃纖維增強劑 與塡充之聚醏樹脂調配物混合後,必須&quot;增稠&quot;以助於處理 。此增稠作用通常係在含有無機驗例如氧化及/氫氧化/ 鎂或鈣之&quot;B-面&quot;中混合而達成。樹脂組成物聚合物上殘留 之羧酸端與驗反應,將其鏈與離子鍵連結,利用增加衆合 物之分子量因而增加其••視黏度&quot;而引入所需之增稠作用。 亭他增稠機制例如聚合物晶化作用或胺酯鍵形成等也可使 用。 下面實例中除非另外陳述,否則所有份數均爲重量比且 -10- 本紙張尺度適用中國國家棟率(CNS ) Λ4現格(210X 297公釐) 裝 訂 1 Ί (請先閱讀背面之注意事項再填寫本頁) 305852 A7 __ B7 五、發明説明(9 ) 爲米制。本文中引用的所有文獻均併入本文以資參考。 實例A、B、C、D、E &amp; F係敘述於片狀模製化合物(SMC) 、塊狀模製化合物(BMC)、和低壓模製化合物(LPMC)中增 進熱塑性低廓形添加劑的表現之各種多封端低衆物改進劑 之製備。 實例A ♦ 改進劑加合物(於實例3、4和5中使用)之製備係利用 循環之衆對酞酸乙二酯碎片輿二乙二醉之酯基轉移作用, 於225至240¾將其浸煮至平均分子量爲約400。此產物具 有羥基鏈端,然後以高油脂肪酸封端之。衆對酞酸乙二醏 之量爲2710克,將1210克之二乙二醇於玻璃樹脂釜中加熱 至240·〇並維持3.5小時。此產物溶於50%丙二醇一甲醚醋 酸酯中,其羥基値介於320和330之間,平均分子量値爲每 個經基170至175。加入6080克高油脂肪酸,以氮喷霧將混 合物加熱至215¾並維持至酸償減少到4至8。此產物爲具 有3000-3500厘泊的黏度之油狀半液體,於100%不揮發物 下使用之。RRI or K. where X ^ 2 where R group can be hydrogen or alkyl group, R is bisphenol A ethylene oxide and / or propylene oxide adduct, phenolic resin ethylene oxide And / or propylene oxide adducts, and cellulosic products and / or their ethylene oxide or propylene oxide adducts. The oligomer of structure II can also be used as the polyol part of these additives, where R can be an alkyl group, a cycloalkyl group, or an aryl group and G is a multifunctional group (yg 2), which can contain an alkyl group, Bonds of aryl, ether, polyether, ester, polyacetate, amide or polyurethane. Also useful are similar multifunctional epoxides, which form multi-capped oligomers, which are obtained from epoxides and acids using nucleophilic addition reactions to obtain esters. In addition, various alkyd resins are also useful in the present invention. Drunken acid is known in this art, see for example Kirk-Othmer, 3rd edition, vol. 2, p.18. Generally, the average molecular weight of these low-profile objects is very low, preferably 2,000 or less. The oligomers are typically planed and compounded.... · · · Printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. However, as long as the specific unsaturated part has low reactivity to styrene, some Unsaturation is allowed. Two or more functional sites in the low profile are easy to connect with long-chain fatty acids with 8 to 22 carbon atoms. Useful C8 to C22 monofunctional acids for reaction with multifunctional oligomers include: lauric acid, linolenic acid, hypolinolenic acid, oleic stearic acid, stearic acid, linseed oleic acid, undecanoic acid, heptadecanoic acid , Crucic acid, palm oleic acid, oleic acid, xin-9 — This paper scale is applicable to China ’s national rate (CNS) A4 specification (210X297 mm) A7 B7 printed by employees ’consumer cooperatives of the Central Bureau of Standards of the Ministry of Economy V. Inventions Description (8) Acid, 2-ethylhexanoic acid, nonanoic acid, capric acid, oleic acid, myristic acid, palmitic acid, arachidic acid, behenic acid, veracic acid, high oil fatty acid, and mixtures thereof . Lauric acid, stearic acid, and high oil fatty acids are preferred acids. The fourth component of the resin system is one or more of olefin-free monomers and polyunsaturated polyimide components. Useful monomers include styrene, methyl methacrylate, divinylbenzene, O (-methylstyrene, vinyl acetate, various alkyl acrylates and alkyl methacrylates, etc. The most commonly used and the best The single skull is stupid. Additional optional ingredients include scale release agents such as stearic acid and calcium stearate, fillers such as calcium carbonate, fly ash, wood powder, mica, glass beads or ceramic beads, curing accelerators For example, organic cobalt compounds, curing initiators such as vinegar peroxide, dialkyl peroxides, alkylaryl peroxides, diaryl peroxides, ketal peroxides, and ketone peroxides. Inhibitors such as butyl Ketoben (BHT), p-benzoquinone (PBQ), hydrogen coupling (HQ), and tetrahydroquinone (THQ) are also optional components. In addition, some simple components such as sheet molding compounds (SMC) ) Or bulk molding compound (BMC), after mixing the glass fiber reinforcement and the polyfilled resin formulation, it must be &quot; thickened &quot; to aid in processing. This thickening effect is usually Such as oxidation and // hydroxide / magnesium or calcium &quot; B-face & qu ot; mixed to achieve. The carboxylic acid end remaining on the polymer of the resin composition reacts with the test, linking its chain with the ionic bond, and increasing the molecular weight of the public compound thereby increasing its viscosity. Thickening effect of tinta, such as polymer crystallization or amine ester bond formation, can also be used. Unless otherwise stated in the following examples, all parts are weight ratios and -10-This paper size applies to China National Building Rate (CNS) Λ4 present grid (210X 297mm) Binding 1 Ί (Please read the precautions on the back before filling out this page) 305852 A7 __ B7 5. The description of invention (9) is metric. All cited in this article The literature is incorporated herein for reference. Examples A, B, C, D, E & F are described in sheet molding compound (SMC), bulk molding compound (BMC), and low pressure molding compound (LPMC ) In the preparation of various multi-capped low-consumer modifiers that enhance the performance of thermoplastic low profile additives. Example A ♦ The preparation of modifier adducts (used in Examples 3, 4 and 5) is based on the use of recycling Ethylene phthalate fragments and diethylene glycol The transesterification effect of the drunkenness was digested from 225 to 240¾ to an average molecular weight of about 400. This product had a hydroxy chain end, which was then capped with a high oil fatty acid. The amount of ethylene diphthalate was 2710 g , 1210 grams of diethylene glycol is heated to 240 · 〇 in a glass resin kettle and maintained for 3.5 hours. This product is dissolved in 50% propylene glycol monomethyl ether acetate, its hydroxyl value is between 320 and 330, the average molecular weight Values are 170 to 175 per base. Add 6080 grams of high-oil fatty acid and heat the mixture to 215¾ with nitrogen spray and maintain until the acidity is reduced to 4 to 8. This product is an oil with a viscosity of 3000-3500 centipoise It is a semi-liquid and it is used under 100% non-volatile matter.

實例B、E和FExamples B, E and F

經濟部中央標隼局員工消費合作社印IL 裝------訂 (請先閱讀背面之注意事項再填寫本頁) 改進劑加合物B(於實例6和9中使用)爲含有己二酸和 二乙二醇之裡基末端低衆物,其兩端以高油脂肪酸封端。 將1828克己二酸和1772克二乙二醇裝入4-升玻璃樹脂釜中 。於氮喷霧下,將溫度緩緩增加到21〇t!,同時除去大約 450克水。當酸價減少到1以下時,經基値爲135-140。 將高油脂肪酸(613克)和887克此低衆物產物裝到2-升玻璃 -11- 本紙張尺度適用中國國家標準(CNS ) A4规格(210X297公釐) A7 B7 ΒΟΓ p气利 83110653«; Φ -&gt;No JI1 !〇653 (Amended A Submitted nn January vO 1007¾ 五、發明説明(|〇 ) 樹脂釜中,將混合液缓缓加熱到210·〇同時除去水至酸價 介於4和8之間。此多封端低聚物改進劑產物爲具有約7〇〇厘 泊的黏度之油狀液體,於1〇〇%不揮發物下使用之。以相 同方法製備出其他添加劑,例如月桂酸加合物低聚物以己 二酸和環己垸二甲醇低聚物製備(加合物E),高油脂肪酸 加合物以環己烷二曱酵低衆物製備(加合物F)。The Ministry of Economic Affairs, Central Standard Falcon Bureau Employee Consumer Cooperative Printed IL Pack --- Order (please read the precautions on the back before filling this page) Improver adduct B (used in Examples 6 and 9) contains The dibasic end of the diacid and diethylene glycol are low-end, and both ends are capped with high oil fatty acids. A 4-liter glass resin kettle was charged with 1828 grams of adipic acid and 1772 grams of diethylene glycol. Under nitrogen spray, the temperature was slowly increased to 21〇t! While removing about 450 grams of water. When the acid value decreases below 1, the base value is 135-140. Load high oil fatty acid (613g) and 887g of this low-end product into 2-liter glass-11- This paper scale is applicable to Chinese National Standard (CNS) A4 specification (210X297mm) A7 B7 ΒΟΓ p 气 利 83110653 « Φ-> No JI1! 〇653 (Amended A Submitted nn January vO 1007¾ V. Description of the invention (| 〇) In the resin kettle, the mixture is slowly heated to 210 · 〇 while removing water to the acid value between 4 and Between 8. The multi-blocked oligomer improver product is an oily liquid with a viscosity of about 700 centipoise, which is used at 100% non-volatile matter. Other additives are prepared in the same way, for example The lauric acid adduct oligomer is prepared from adipic acid and cyclohexane dimethanol oligomer (adduct E), and the high oil fatty acid adduct is prepared from cyclohexane dihydrogen fermentation adduct (adduct) F).

實例C 改進劑加合物C (於實例1、2和3中使用)之製備係將雙 酚A與環氧乙垸和環氧丙垸(SYNF AC⑧8026,得自Mil 1 iken Chemical Co.)之反應產物以硬脂脂肪酸封端而成。將449 克硬脂酸和222克SYNFAC® 8026乙氧基化/丙氧基化雙酚A 以及0.07克FASCAT® 4100單水合化丁基氧化錫衆合作用催 化劑(M &amp; T Chemicals)裝入卜升玻璃樹脂釜中。充分挽 拌下,將混合液加熱至200·〇。所得酯產物爲晶型固體, 將其溶於苯乙烯中,75%不揮發物下,於實例1、2、和3 中使用。Example C The modifier adduct C (used in Examples 1, 2 and 3) was prepared by combining bisphenol A with ethylene oxide and propylene oxide (SYNF AC⑧8026, available from Mil 1 iken Chemical Co.) The reaction product is end-capped with stearic fatty acid. Load 449 grams of stearic acid and 222 grams of SYNFAC® 8026 ethoxylated / propoxylated bisphenol A and 0.07 grams of FASCAT® 4100 monohydrated butyltin oxide mass-co-catalyst (M &amp; T Chemicals) Bu Sheng glass resin kettle. With full stirring, the mixture is heated to 200 · 〇. The resulting ester product was a crystalline solid, which was dissolved in styrene at 75% non-volatiles and used in Examples 1, 2, and 3.

實例D 改進劑加合物D以多官能環氧化合物和高油脂肪酸製成 。將594克高油脂肪酸和394克Epon 828雙環氧樹脂(Shell Chemical)裝入卜升玻璃樹脂釜中。再裝入約2.4克 Aerojet Accelerator AMC-2 鈷複合物催化劑(Aer〇jet Chemical Operations,Sacramento,California)。充分攪 拌下,將混合液加熱至150’C 1 1/2至2小時。此經g旨產 物於實例3中使用(100%不揮發物)。 -12- 本紙張尺度適用中國國家標準(CNS ) Λ4規格(210x 297公锋) (請先閲讀背面之注意事項再填寫本頁) 、\έ 丁 經濟部中央標準局員工消費合作社印製 B7 五、發明説明(11)Example D Modifier adduct D is made with multifunctional epoxy compounds and high oil fatty acids. A liter glass resin kettle was charged with 594 grams of high oil fatty acid and 394 grams of Epon 828 double epoxy resin (Shell Chemical). About 2.4 grams of Aerojet Accelerator AMC-2 cobalt complex catalyst (Aerojet Chemical Operations, Sacramento, California) was then charged. With sufficient stirring, the mixture is heated to 150'C 1 1/2 to 2 hours. This product was used in Example 3 (100% non-volatile matter). -12- This paper scale is applicable to the Chinese National Standard (CNS) Λ4 specification (210x 297 male front) (please read the precautions on the back before filling out this page), printed by B7, Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 、 Instructions for invention (11)

實例G 晶型基底樹脂 有幾個晶型基底樹脂被製備和於一些實例中使用,其係以 反丁烯二酸(FA)和新戊基乙二醇(NPG)製備並以丙二醇(PG) 或丙二酵(PG)與乙二醇(EG)之摻合物加以修飾。使用6至 10%莫耳過量之乙二醇下,將反應物加熱到140-C和195¾ 之間,除去水至酸償爲每克試樣之KOH毫克數爲28-32。然 後將生成的不飽和聚酯樹脂於抑制苯乙烯中減至不揮發物 65%。 實例 於下面實例1中,將改進劑加到含有AROPOL Q8000飽和 聚酷低麻形添加劑(Ashland Chemical Company,Division of Ash 1 and 0 i 1,1 nc .,Co 1 umbus,Oh i o 出售)之系統中。 ---------^------IT------/ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作杜印製 -13- 本紙張尺度適用中國國家標準(CNS ) A4规格(210X297公釐) 305852 Μ Β7 五、發明説明(12 ) 經濟部中央標準局員工消費合作社印製 實例1 成分 調配物#1 調配物#2 調配物#3 調配物#4 (phr) (phr) (phr) (phr) 晶型基底樹脂1 74.0 75.5 75.5 77.0 Q8000胺酯交聯 飽和聚S旨低廓形 添加劑 20.0 18.0 18.0 16.0 苯乙烯 4.0 1.5 0.5 1.0 甲基丙烯酸甲醏 2.0 2.0 2.0 2.0 丁基m基甲苯(BHT) 0.08 0.08 0.08 0.08 VDI钴加速劑2 0.1 0.1 0.1 0.1 碳酸鈣塡充劑 150.0 150.0 150.0 150.0 Perkadox 16 過氧 引發劑3 0.5 0.5 0.5 0.5 L-256過氡引發劑4 1.5 1.5 15 1.5 Ethox® DL-14 5 - 3.0 — — 相容性添加劑 不相容性改進劑 加合物C 6 ~ - 4.0 4.0 Barco 1硬度 • 34.8 26.3 31.8 36.2 基f變化 -1.0 -0.3 +0.5 0.0 密耳/吋 收縮 收縮 膨脹 沒有變化 -14- 一請先閱讀背面之注意事項再填寫本頁) -9 本紙張尺度適用中國國家標率(CNS ) A4規格(210X297公釐) A7 B7 經濟部中央標準局貝工消費合作社印製 五、發明説明(13) 於調纪物3和4中,比調配物1使用較少的LPA,其不 相容性改進劑加合物C之使用將Barco丨硬度之減少減至最 小程度(參照調釔物2中之相容性物質)並表現增進之收培 控制。調配物2 ’含有相容性改進劑Ethox DL-14界面活性 劑’改良收缩控制,但是有害地將Barcol硬度降低23%。 1晶型樹脂係以100/60/40莫耳比率之反丁烯二酸/ 靳戊基乙 二 醇/丙二醇予以製備。酸償28至32,於苯乙烯 中不揮發物65%。 2有機酸鈷鹽(12%金屬)得自Mooney Chemicals 3 得自 Akzo America,Inc. 4 得自 Atochem North America, Inc. 5衆乙二醇二月桂酸醏,EO片段Mn 600,得自Ethox Chemicals, Inc. 6以二硬脂酸酯封端之低聚物,如實例C所述予以製備 -15 本紙張尺度適用中國國家樣準(CNS &gt; A4規格(21〇Χ297公釐) 經濟部中央橾準局員工消費合作杜印製 A7 B7 五、發明説明(14) 於下面實例2中,於含有晶型基底樹脂、Ashland Chemical丨nc.所售的Uralloy®雜化樹脂LPNT低廓形添加 劑和二環戊二烯非晶型基底樹脂之低廓形模製化合物中使 實例2 成 分 調配物#1 *調配物#2 (ph£i- (phr) 晶型1基底樹脂 71.0 72.5 Uralloy LPNT雜化樹脂 25.0 17.5 低廓形2添加劑 加合物C 3 -- 4.0 DCPD非晶型基底樹脂4 2.〇 2.0 甲基丙烯酸甲醏 2.〇 2.0 丁基羥基甲苯(BHT) 0.08 0.08 碳酸鈣填充劑 150.0 150.0 Perkadox 16過氧引發劑 0.5 0.5 L-256過氧引發劑 1.5 Barcol硬度 14.7 35.8 基質收缩性密耳/吋 -0.4 -0.4 於調配物#2中,不相容性改進劑之使用使Barc〇l硬度戲 劇性地增進而仍維持收繪控制,因而説明本發明多封端低 物改進劑與胺醏低聚物低廓形添加劑一起使用之有效性 如實例1備註1之相同樹脂 -16 本紙張凡度適用中國國家榡率(CNS ) A4規格(210X297公釐) _a^i 1 H ---1 m m - —^i --eJ (請先閱讀背面之注意事項再填寫本頁) A7 _B7___ 五、發明説明(15 ) 2 Ashland Chemical所售之衆胺酯LPA,於苯乙歸中不 揮發物40% 3如實例C所述製備之硬脂酸二封端乙氧基化丙氧基化 雙酚A不相容性改進劑 4 Ashland Chemical, Inc.產品AROPOL 8014 :於苯乙烯 中不揮發物72-75%,酸償18-35,史托克黏度10-12 ----------^------1T------J (請先閱讀背面之注意事項再填寫本頁)Example G Crystal base resin Several crystal base resins were prepared and used in some examples, which were prepared with fumaric acid (FA) and neopentyl glycol (NPG) and propylene glycol (PG) Or modified by a blend of malonanase (PG) and ethylene glycol (EG). Using 6 to 10% molar excess of ethylene glycol, the reaction was heated to between 140-C and 195¾, and water was removed until the acid was 28-32 mg KOH per gram of sample. The unsaturated polyester resin formed was then reduced to 65% of non-volatile matter in styrene suppression. Example In Example 1 below, the improver was added to a system containing AROPOL Q8000 saturated poly cool low hemp-shaped additives (Ashland Chemical Company, Division of Ash 1 and 0 i 1,1 nc., Co 1 umbus, sold by Ohio) in. --------- ^ ------ IT ------ / (Please read the precautions on the back before filling in this page) The Ministry of Economic Affairs Central Standards Bureau Beigong Consumer Cooperation Du Printed- 13- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 305852 Μ Β7 V. Description of invention (12) Printed example of the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 1 Ingredient Blend # 1 调配 物 # 2 Formulation # 3 Formulation # 4 (phr) (phr) (phr) (phr) Crystalline base resin 1 74.0 75.5 75.5 77.0 Q8000 urethane cross-linked saturated poly-S low profile additive 20.0 18.0 18.0 16.0 Styrene 4.0 1.5 0.5 1.0 Methacrylic acid methacrylate 2.0 2.0 2.0 2.0 Butyl m-toluene (BHT) 0.08 0.08 0.08 0.08 VDI cobalt accelerator 2 0.1 0.1 0.1 0.1 Calcium carbonate filler 150.0 150.0 150.0 150.0 Perkadox 16 Peroxy initiator 3 0.5 0.5 0.5 0.5 L-256 Over Radon Initiator 4 1.5 1.5 15 1.5 Ethox® DL-14 5-3.0 — — Compatibility Additive Incompatibility Improver Adduct C 6 ~-4.0 4.0 Barco 1 Hardness • 34.8 26.3 31.8 36.2 Base f change -1.0 -0.3 +0.5 0.0 mil / inch shrinkage shrinkage expansion has no change -14- Please read the precautions on the back before filling in this page) -9 This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) A7 B7 Printed by Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 3. Description of the invention (13) In the regulators 3 and 4, less LPA is used than the regulator 1, and the use of the incompatibility improver adduct C minimizes the reduction of Barco hardness (refer to Yttrium 2 compatible substances) and show enhanced harvest control. Formulation 2 'contains a compatibility modifier Ethox DL-14 surfactant' which improves shrinkage control, but deleteriously reduces Barcol hardness by 23%. The 1-crystalline resin was prepared with a ratio of 100/60/40 moles of fumaric acid / pentyl glycol / propylene glycol. Acid compensation 28 to 32, 65% non-volatile in styrene. 2 Organic acid cobalt salt (12% metal) from Mooney Chemicals 3 From Akzo America, Inc. 4 From Atochem North America, Inc. 5 Diethylene glycol dilaurate, EO fragment Mn 600, from Ethox Chemicals , Inc. 6 oligomer capped with distearate, prepared as described in Example C-15 This paper scale is applicable to China National Standards (CNS &gt; A4 specification (21〇Χ297mm) Central Ministry of Economic Affairs A7 B7 is produced by consumer cooperation of the Ministry of Industry and Commerce. V. Description of the invention (14) In Example 2 below, Uralloy® Hybrid Resin LPNT Low Profile Additives containing crystalline base resin, Ashland Chemical 丨 nc. In the low profile molding compound of dicyclopentadiene amorphous base resin, Example 2 is used. Component formulation # 1 * Formulation # 2 (ph £ i- (phr) Crystal form 1 base resin 71.0 72.5 Uralloy LPNT hybrid Resin 25.0 17.5 Low profile 2 additive adduct C 3-4.0 DCPD amorphous base resin 4 2.〇2.0 Methacrylic acid methacrylate 2.0.2.0 Butylhydroxytoluene (BHT) 0.08 0.08 Calcium carbonate filler 150.0 150.0 Perkadox 16 peroxy initiator 0.5 0.5 L-256 peroxy initiator 1.5 Barcol hardness 14.7 35.8 Matrix shrinkage mil / inch -0.4 -0.4 In formulation # 2, the use of an incompatibility improver causes Barc〇l hardness to increase dramatically while still maintaining drawing control, thus illustrating the present invention The effectiveness of the multi-end low-end modifiers and amine dimer oligomer low profile additives is the same as the resin in Example 1 Remark 1-16 This paper is generally applicable to the Chinese national standard rate (CNS) A4 specifications (210X297 mm ) _A ^ i 1 H --- 1 mm-— ^ i --eJ (Please read the precautions on the back before filling in this page) A7 _B7___ 5. Description of the invention (15) 2 Public amine ester LPA sold by Ashland Chemical , 40% non-volatile matter in phenethyl acetone 3 Stearic acid dicapped ethoxylated propoxylated bisphenol A incompatibility improver prepared as described in Example C 4 Ashland Chemical, Inc. product AROPOL 8014: 72-75% of non-volatile matter in styrene, acid compensation 18-35, Stoke viscosity 10-12 ---------- ^ ------ 1T ----- -J (please read the notes on the back before filling this page)

經濟部中央搮準局貝工消費合作社印I -17 - 本紙張尺度適用中國國家棣隼(CNS&gt;A4规格(210X297公釐) 505832 五、發明説明(w) 實例3中,於含有晶型基底樹脂65%不揮發物之低壓模 製化合物(LPMC)中使用本發明的三個多封端低衆物改進劑 °Q8000低廓形添加劑爲Ashland Chemical所售’經改良 之基底樹脂八1{〇?01&gt;8014二環戊二烯(1)以0)爲45111311(1 Chemical所售,於 194卞(90*(〇)模製。 (請先閱讀背面之注意事項再填寫本頁) ,1Τ 經濟部中央橾準局員工消t合作社印製 -18 - 本紙張尺度適用中國國家榡率(CNS ) A4也格(210X297公釐) 經濟部中央櫟率局員工消費合作社印製 A7 B7 五、發明説明(17 ) 實例3 成分 調配物#1 調配物#2 調配物#3 調配物#4 (phr) (phr) (phr) (phr) 晶型基底樹脂1 73.0 73.0 73.0 76.0 Q8000飽和聚酯 低廓形添加劑 17.0 17.0 17.0 20.0 加合物C 2 4.0 - - - 加合物D 3 - 3.0 - - 加合物A 4 - - 3.0 - DCPD非晶型基底 2.0 2.0 2.0 2.0 樹脂5 苯乙烯 2.0 3.0 2.0 - 甲基丙烯酸甲酯 2.0 2.0 2.0 2.0 丁基m基甲苯 0.08 0.08 0.08 0.08 碳酸转填充劑 150.0 150.0 150.0 150.0 Perkadox 過氧 0.5 0.5 0.5 0.5 引發劑 L-256過氡引發劑 1.5 1.5 15 1.5 Barcol硬度 39.4 40.1 41.4 42.0 基質收縮性 0 -0.5 +0.4 -0.5 (.密耳/吋) 無 收縮 膨脹 收縮 -19 - 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) --------‘裝-- (請先閲讀背面之注意事項再填寫本頁)Ministry of Economic Affairs, Central Bureau of Economic and Trade, Beigong Consumer Cooperatives Printed I -17-This paper scale is applicable to China ’s National Falcon (CNS> A4 specification (210X297 mm)) 505832 5. Description of invention (w) In Example 3, it contains a crystalline substrate The three multi-block low-modifier improvers of the present invention are used in low-pressure molding compounds (LPMC) of 65% non-volatile resins. The Q8000 low profile additives are sold by Ashland Chemical's' modified base resin eight 1 {〇 ? 01 &gt; 8014 dicyclopentadiene (1) 0) is 45111311 (sold by 1 Chemical, molded at 194 Bian (90 * (〇). (Please read the precautions on the back before filling this page), 1Τ Printed by the Staff Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs -18-This paper scale is applicable to the Chinese national rate (CNS) A4 (210X297 mm). The A7 B7 is printed by the Staff Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs. Description (17) Example 3 Ingredient formulation # 1 Blend # 2 Blend # 3 Blend # 4 (phr) (phr) (phr) (phr) Crystalline base resin 1 73.0 73.0 73.0 76.0 Q8000 saturated polyester low profile Additive 17.0 17.0 17.0 20.0 Adduct C 2 4.0---Adduct D 3- 3.0--Adduct A 4--3.0-DCPD amorphous substrate 2.0 2.0 2.0 2.0 Resin 5 Styrene 2.0 3.0 2.0-Methyl methacrylate 2.0 2.0 2.0 2.0 Butyl m-toluene 0.08 0.08 0.08 0.08 Carbonated transfer filling Agent 150.0 150.0 150.0 150.0 Perkadox Peroxy 0.5 0.5 0.5 0.5 Initiator L-256 Over Radon Initiator 1.5 1.5 15 1.5 Barcol Hardness 39.4 40.1 41.4 42.0 Matrix Shrinkage 0 -0.5 +0.4 -0.5 (.mil / inch) No shrinkage Expansion and Shrinkage -19-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) -------- 'installation-- (Please read the precautions on the back before filling this page)

、1T A 7 B7 五、發明説明(1 8 ) 調配物1、2和3較調配物4含有更少的飽和衆S|LPA。 三個不同的改進劑,取代部分的飽和聚酯LPA,提供相同 的硬度和相等或増進之收縮控制。 ~ 一·. 1晶型樹脂係以100/60/30/ 10莫耳比率之反丁婦二 酸/新戊基乙二醇/丙二醇/乙二醇予以製備。酸償28至 32,於苯乙烯中不揮發物65%使用之。 2以二硬脂酸醋封端之低衆物改進劑,如實例C所述予 以製備 3以二高酸畴(ditallate)封端之低衆物改進制,如實 例D所述予以製備 4以二高酸酯封端之低衆物改進劑,如實例A所述予以 製備 5 AR0P0L 8014 --------裂------訂------i (請先閱讀背面之&gt;i意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 -20 - 本紙張疋度適用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中央橾準局員工消費合作社印裝 Ο · r- Γ- ο υ 5 6 ο 2 Α7 Β7 五、發明説明(19 ) 實例4示出於194T(90eC)模製的低廓形模製化合物中 ,3個不同的多封端低聚物改進劑之使用。 -21 - n- n^i HI ^^^1 nn n^i m In ^in ^^1 n^— J,J 芽 Λ5 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 五、發明説明(20 ) 1 2 3 办 5 6, 1T A 7 B7 V. Description of the invention (1 8) Formulations 1, 2 and 3 contain less saturated S | LPA than formulation 4. Three different modifiers, replacing part of the saturated polyester LPA, provide the same hardness and equal or progressive shrinkage control. ~ 1 · .1 crystalline resin is prepared with a ratio of 100/60/30/10 moles of fumaric acid / neopentyl glycol / propylene glycol / ethylene glycol. Acid compensation 28 to 32, use 65% of non-volatile matter in styrene. 2 Modified with low stearic acid end capped with distearic acid vinegar, prepared as described in Example C 3 Prepared with an improved low end substance with two high acid domain (ditallate) capped, prepared as described in Example D 4 Dihigherate-terminated low-modifier improver, prepared as described in Example A 5 AR0P0L 8014 -------- Crack ------ Order ------ i (Please read first The back of the page &gt; i will fill in this page again) Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -20-This paper is applicable to the Chinese National Standard (CNS) A4 (210X297mm) Central Ministry of Economic Affairs Printed by employee consumer cooperatives Ο · r- Γ- ο υ 5 6 ο 2 Α7 Β7 V. Description of the invention (19) Example 4 is shown in the low profile molding compound molded in 194T (90eC), 3 different Use of multi-end oligomer modifier. -21-n- n ^ i HI ^^^ 1 nn n ^ im In ^ in ^^ 1 n ^ — J, J bud Λ5 (please read the precautions on the back before filling this page) This paper size is applicable to China Standard (CNS) A4 specification (210X297mm) 5. Description of invention (20) 1 2 3 Office 5 6

CO CO cn OO CD CO COCO CO cn OO CD CO CO

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CD I—» 激涔棼2(phr) TO~~ -17.6 — 12.0 -10.2 -0.5 -1.5 -0·9 _蝎斧翁详(输Ι-Η/Ι4) 10.0 12.0 20.8 1.0 150 0.5 1·5 760 激界棼#2 iphr) 10.D 12.0 2 0.8 1.0 】50 0.5 1.5 76.0 畤皆μ 湓拷棼#3 (phr) 經濟部中央標準局員工消費合作社印製 -^p^丨焊~旗尊(phase out) ,新冰_磷啩^扣办陟铱捃棼If ο ^泠3 —焊.^恭赛-贫冰_1r-a-4^φπ择辞棼蝎。 y^y丨焊~旗恭贫方_1r ^振!i#'1r。 φ€** 斜;^-旗^—弹。·· ^押*^-费丨焊。 φ€* -旗费!ϋ。 · 2.0 to 0.8 1·0 150 0.5 1,5 17.0 3.5 760 湓涔棼#4 (phr) 裝 訂 ^ (請先閱讀背面之注意事項再填寫本頁) 760 17.0 3.5 2.0 Co 000 1·〇 150 0.5 1.5 湓搾聲#5 iphr) 3·5 2·0 1 0.8 1.0 150 0.5 1.5 17·0 76.0 湓搾棼#6 iphr) 本紙張尺度適用中國國家橾準(CNS ) Α4规格(210Χ297公釐) -22- A7 B7 五、發明説明(21 ) 調物1、2和3只含增進加合物而表現整體收縮性,顯示 單獨使用時,加合物五爲低廓形添加劑。調配物4、5和6 分别含有加合物A、E和F及Q8000飽和聚酯LPA,顯示優越 之收縮控制。 1晶型樹脂係以100/60/30/10莫耳Λ率之反丁歸二 酸/新戊基乙二醇/丙二醇/乙二酵予以製備。酸償28至 32,於苯乙烯中不揮發物爲65%使用之。 2實例Α製備之二高酸醏封端之低聚物 3實例E製備之二高酸酯封端之低衆物 4實例F製備之二高酸s旨低聚物 5 得自 Specialty Products Co.之 Specialty 102 i -裝 訂 線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印袋 -23- 本紙張尺度適用中國國家揉準(CNS ) A4規格(210X297公釐) 五、發明説明(22 7 Β 經濟部中夹埭隼局員工消費合作社印裂CD I— »Agitated 2 (phr) TO ~~ -17.6 — 12.0 -10.2 -0.5 -1.5 -0 · 9 _Scorpion Axe Weng (loss Ι-Η / Ι4) 10.0 12.0 20.8 1.0 150 0.5 1.5 760 激 界 棼 # 2 iphr) 10.D 12.0 2 0.8 1.0】 50 0.5 1.5 76.0 畤 都 μ 湓 Copy 棼 # 3 (phr) Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs- ^ p ^ 丨 Welding ~ Qizun (phase out), new ice_phosphorus ^ buckle to do it if ο ^ Ling 3-welding. ^ Gong Sai-poor ice _1r-a-4 ^ ππ selective speech scorpion. y ^ y 丨 Welding ~ Qi Gong poor side_1r ^ Vibration! i # '1r. φ € ** oblique; ^ -flag ^-bomb. ·· ^ charge * ^-fee 丨 welding. φ € *-flag fee! ϋ. 2.0 to 0.8 1 · 0 150 0.5 1,5 17.0 3.5 760 湓 攔 棼 # 4 (phr) Binding ^ (please read the notes on the back before filling this page) 760 17.0 3.5 2.0 Co 000 1 · 〇150 0.5 1.5湓 压 声 # 5 iphr) 3 · 5 2 · 0 1 0.8 1.0 150 0.5 1.5 17 · 0 76.0 湓 掼 棼 # 6 iphr) This paper scale is applicable to China National Standards (CNS) Α4 specifications (210 × 297 mm) -22 -A7 B7 V. Description of the invention (21) The blends 1, 2 and 3 contain only adducts to enhance the overall shrinkage, showing that when used alone, adduct 5 is a low profile additive. Formulations 4, 5 and 6 contain adducts A, E and F and Q8000 saturated polyester LPA, respectively, showing superior shrinkage control. The 1-crystalline resin was prepared with a ratio of 100/60/30/10 moles of fumaric acid / neopentyl glycol / propylene glycol / glyoxan. Acid compensation 28 to 32, the non-volatile content in styrene is 65%. 2 Example A prepared dicapric acid-capped oligomer 3 Example E prepared dicaprate-capped oligomer 4 Example F prepared diacid oligomer 5 was obtained from Specialty Products Co. Specialty 102 i-binding line (please read the precautions on the back before filling in this page) Printed Bag for Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs-23- This paper size is suitable for China National Standard (CNS) A4 (210X297mm ) 5. Description of the invention (22 7 Β Printed by the Consumer Consumption Cooperative of the Zhongjiadai Falcon Bureau of the Ministry of Economic Affairs

Barcol硬度 ^ ^ ^ v^i 〇 i i 1 1 ffi 00 敢 必 &gt;—i Cv i »—4 )—i I. fw 〇 &lt;2p 一 cn 你·一^CJi 私私 Jl ra O· 雖 = 逢 p - Dtr ^ N5 成分 實例5 + &lt;3&gt; CO cr&gt; 1»»·&gt; ΟΊ i1 *&lt;] i» O &lt;3&gt; CO CO OO . · · 1 1 1 1 1..... cn cn&lt;3) cncr&gt;cncDCi&gt; 1 &lt;3&gt; 〇〇 CO oo 73.0 17.0 4.5 2.0 3.5 150.0 0.5 1.5 CO 1 〇 〇〇 CO CO 73.0 17.0 4.5 2.0 3.5 150.0 0.5 1.5 二赛 S +0.07 CO &lt;y&gt; CO 73.0 17.0 4.5 2.0 3.5 150.0 0.5 1.5 調配物#4 (phr) 1 &lt;3* CO oo 73.0 17.0 4.5 2.0 3.5 150.0 0.5 1.5 CJ1 24.0 73.0 17.0 4.5 2.0 3.5 150.0 0.5 1.5 1 CO - 33.5 1- t__j ΟΊ ^ *—*〇&gt;〇&gt; ro cn co • · 1 1 1 1 1 1 · · * · CJ1 CJl &lt;〇 〇&gt;〇&gt;〇&gt;〇 --Ν «S3 崎玄5^'&amp;滋 gtAsh 1 and Chemi ca 1SQ8000摩甘辦蟲#;,;#^势^逢^§0睹 _ 辦聲録埤咎涔斜&gt;鹈 '和斜啷ill·録邻热舛鹈~迕鹈庚辨棼涔搽逡iusji。 (請先閱讀背面之注意事項再填寫本頁) 秦· 、-=* Γ .丨绍 本紙張尺度適用中國國家標準(CNS &gt; A4規格(210X297公釐) -24- Α7 Β7 305852 五、發明説明(23) 注意添加劑ML-14、DL-14 ' T0-16和DT0-14均具有聚乙 二酵之中心片段。此實例示出以高油脂肪酸將添加劑單封 端比不封端得到較小的收縮性,二封端得到膨脹而非收縮 。同時注意加合物A係以高油脂肪酸二封端。 1如實例3之相同基底樹脂 2飽和聚酯低廓形添加劑,50%不揮發物,Ashland Chemi ca1, Inc . 3實例A製備之二高酸醋封端之低聚物 4分子量400之衆乙二醇,得自Dow Chemical Co. 5得自Ethox Chemical, Inc.之聚乙二醇一月桂酸醏(平 均分子量値約600之E0片段(Μη))相容性添加劑 6得自Ethox Chemical,Inc.之衆乙二酵二月桂酸酷(Ε0 片段Μη约600)相容性添加劑 7得自Ethox Chemical,Inc.之聚乙二醇一高酸醏(Ε0片 段Μη約600)相容性添加劑 8得自£1:11(^(:1^111卜31,111(:.之聚乙二醇二高酸醋(£0片 段Μη約600)不相容性添加劑 --------I -- (請先閱讀背面之注意事項再填寫本頁) 、-'0Barcol hardness ^ ^ ^ v ^ i 〇ii 1 1 ffi 00 dare to> &gt; —i Cv i »—4) —i I. fw 〇 &lt; 2p one cn you one ^ CJi 私 私 Jl ra O · Although = Every p-Dtr ^ N5 Component Example 5 + &lt; 3 &gt; CO cr &gt; 1 »» · &gt; ΟΊ i1 * &lt;] i »O &lt; 3 &gt; CO CO OO. · 1 1 1 1 1 ... .. cn cn &lt; 3) cncr &gt; cncDCi &gt; 1 &lt; 3 &gt; 〇〇CO oo 73.0 17.0 4.5 2.0 3.5 150.0 0.5 1.5 CO 1 〇〇〇CO CO 73.0 17.0 4.5 2.0 3.5 150.0 0.5 1.5 Second S +0.07 CO &lt; y &gt; CO 73.0 17.0 4.5 2.0 3.5 150.0 0.5 1.5 formulation # 4 (phr) 1 &lt; 3 * CO oo 73.0 17.0 4.5 2.0 3.5 150.0 0.5 1.5 CJ1 24.0 73.0 17.0 4.5 2.0 3.5 150.0 0.5 1.5 1 CO-33.5 1- t__j ΟΊ ^ * — * 〇 &gt; 〇 &gt; ro cn co • · 1 1 1 1 1 1 1 · · * · CJ1 CJl &lt; 〇〇 &gt; 〇 &gt; 〇 &gt; 〇--Ν «S3 崎 玄 5 ^ '& zigtAsh 1 and Chemi ca 1SQ8000 摩 甘 办 虫 #;,; # ^ 势 ^ 逢 ^ §0 見 _ 許 記录 柤 擔 气 气 &gt; pelican and oblique ill ~ Pei Geng discerns iusji. (Please read the precautions on the back before filling in this page) Qin ·,-= * Γ. This paper size is applicable to Chinese national standards (CNS & A4 specifications (210X297 mm) -24- Α7 Β7 305852 5. Invention Explanation (23) Note that the additives ML-14, DL-14 'T0-16 and DT0-14 all have a central segment of polyethylene glycol fermentation. This example shows that the use of high-oil fatty acids for the single end capping of the additive is more effective than the non-end capping. Small shrinkage, the second end is expanded instead of shrinking. At the same time, note that Adduct A is end-capped with high oil fatty acid. 1 The same base resin as in Example 3 2 Saturated polyester low profile additive, 50% non-volatile 3, Ashland Chemi ca1, Inc. 3 Example A prepared two high-acid vinegar-terminated oligomers 4 molecular weight 400 zhong ethylene glycol, obtained from Dow Chemical Co. 5 obtained from Ethox Chemical, Inc. polyethylene Alcohol monolaurate (E0 segment (Μη) with an average molecular weight value of about 600) compatibility additive 6 is available from Ethox Chemical, Inc., Glyphosate Dilaurate (E0 segment Μη about 600) compatibility additive 7 Compatible addition of polyethylene glycol monoperoxylate (E0 fragment Mn about 600) from Ethox Chemical, Inc. 8 from £ 1: 11 (^ (: 1 ^ 111 Bu31,111 (:. polyethylene glycol diacid vinegar (£ 0 fragment Mn about 600) incompatible additives ------ -I-(Please read the precautions on the back before filling in this page), -'0

I 經濟部中央標準局員工消費合作社印11 本紙張尺度適用中’國國家榡準(CNS &gt; A4規格(210X297公釐) A7 B7 經濟部中央標準局員工消費合作杜印裝 五、發明説明(24) 實例6敘述含有非晶型不飽和聚酯基底樹脂、三個不同 低廓形添加劑和改進劑加合物B之SMC調配物。 —26 — n- ^^1 nn an— n^i n^— IF nn n^i nn· i tn--SJ (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家梂準(CNS ) A4規格(210X297公釐) 經濟部中央樣隼局員工消费合作社印製 五、發明説明(25 ) 實例6 成分 1 2 3 4 5 6 AROPOL Q6585 1 65.0 69.0 59.0 71.1 60.0 60.0 衆醋酸乙烯醏 35.0 25.0 - - - - LPA(40%NV) 聚甲基丙烯酸甲 - - 41.0 23.7 - - S 旨 LPA(31.5%NV) Ura丨loy®雜化樹 - - - - 40.0 30.0 脂2035 LPA(40%NV) 加合物B 一 4.0 - 3.9 - 4.0 苯乙烯 0 2.0 - - — 6.0 高油脂肪酸 1.0 - 1.0 一 0.5 - VDI结加速劑 0.1 0.1 0.1 0.1 0.1 0.1 丁基躍基甲苯 0.1 0.1 0.1 0.1 0.1 0.1 第三丁基過氧苯 1.5 1.5 1.5 1.5 1.5 1.5 甲酸酯 塡充劑 180.0 180.0 150.0 150.0 200.0 200.0 硬脂酸鋅 4.5 4.5 5.5 5.5 4.5 4.5 MgO 2增稠劑 2.3 2.5 2.5 2.7 3.9 3.9 表面品質之Ash land 87 65 116 107 74 57 指數 1非晶型不飽和聚醏樹脂(丙二醇和順丁烯二酸),酸價 28至32,於苯乙烯中不揮發物65%,得自Ashland Chemical Company 2 MgO於低AV不飽和聚醏中之33%分散體 (請先閱讀背面之注$項再填寫本頁) -裝·I The Ministry of Economic Affairs, Central Bureau of Standards, Employee Consumer Cooperative Printed 11 This paper standard is applicable to China's national standards (CNS &A; A4 specifications (210X297 mm) A7 B7 The Ministry of Economic Affairs, Central Bureau of Standards, Employee Consumption Cooperation Du Printed Fifth, invention description ( 24) Example 6 describes an SMC formulation containing an amorphous unsaturated polyester base resin, three different low profile additives and an improver adduct B. —26 — n- ^^ 1 nn an— n ^ in ^ — IF nn n ^ i nn · i tn--SJ (please read the precautions on the back before filling in this page) This paper size is applicable to China National Standards (CNS) A4 specification (210X297mm) Central Falcon Bureau of the Ministry of Economic Affairs Printed by Employee Consumer Cooperative V. Description of the invention (25) Example 6 Ingredients 1 2 3 4 5 6 AROPOL Q6585 1 65.0 69.0 59.0 71.1 60.0 60.0 Vinyl acetate 35.0 25.0----LPA (40% NV) Polymethacrylic acid A--41.0 23.7--S purpose LPA (31.5% NV) Uraloy® hybrid tree----40.0 30.0 fat 2035 LPA (40% NV) adduct B-4.0-3.9-4.0 styrene 0 2.0 --— 6.0 High oil fatty acid 1.0-1.0 One 0.5-VDI junction accelerator 0.1 0.1 0.1 0.1 0.1 0.1 Butyl hoptoluene 0.1 0.1 0.1 0.1 0.1 0.1 Third butyl peroxybenzene 1.5 1.5 1.5 1.5 1.5 1.5 Formate filler 180.0 180.0 150.0 150.0 200.0 200.0 Zinc stearate 4.5 4.5 5.5 5.5 4.5 4.5 MgO 2 thickener 2.3 2.5 2.5 2.7 3.9 3.9 Surface quality Ash land 87 65 116 107 74 57 Index 1 Amorphous unsaturated poly (polypropylene glycol and maleic acid), acid value 28 to 32, in benzene 65% of non-volatile matter in ethylene from 33% dispersion of Ashland Chemical Company 2 MgO in low AV unsaturated polymer (please read note $ on the back and fill in this page)

、1T 線 本紙張尺度適用中國國家橾率(CNS &gt; Α4洗格(210Χ297公釐&gt; 一27 _ A7 3υ5652 五、發明説明(以) 實例6顯示本發明改進劑加合物b在使用三個不同的低 廓形添加劑和非晶型不飽和聚酯樹脂系的SMC調配物中之 效能。 實例7使用以二乙二醇和固化的不飽和衆醏樹脂間之醣 解反應製造之多官能多元醇,以兩個至六個高油脂肪酸分 子封端並具有各種不飽和量之順丁稀二野。 將得自片狀模製化合物之固化聚醋-苯乙烯共聚物與二 乙二醇反應。從產物汽提過量的乙二醇至羥基値爲约505 ,意指羥基當量111爲止。然後在含有0.1%重量比Fascat 4100催化劑(得自M&amp;T Chemicals之水合單丁基氧化錫)之 反應瓶中將一當量乙二醇與一當量高油脂肪酸合併。於 1901〇-2101〇將混合液反應約6.5小時,最终酸價爲4.6。 此產物命名加合物GP-1。 加合物GP-2係以羥基値399(當量重141)之汽提醣解產物 製備的。將一當量之此多元醇與2/3當量重之高油脂肪酸 (當量重286)、1/3當量重之順丁烯二酑與二環戊二烯反 應產物(當量重260)(接著將其異構化爲反丁烯二酸異構物 )、和0.1%重量比之Fascat 4100裝塡入反應瓶中。於 19〇C_21〇C將混合液反應2-3小時,最終酸價爲了。 加合物GP_3和GP_4係以經基値399(當量重141)之汽提酷 解產物製備的。當一當量之此多元鞟與2/3當量重之高油 脂肪酸(當量重286)及0.1%重量比之Fascat ^⑼於丨⑽^ -19(TC反應3.5小時,最終酸價爲2。其—半產物置於一旁 ,命名GP-3。其绰的,含有約1/6莫耳當量羥基化合物, 與1/6莫耳順丁烯二肝於12(TC-U(rc反應2 5小時。當產 物的紅外線分析頚示未殘留順丁烯二酐,即終止反應。 -28- * 本紙張尺度適用中國國家標準(CNS ) .M規格(210X2*^公缝) n^i m m· ί ί 1^1 ^in m ml m 1J 、\έ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 j, B7 五、發明説明(&gt;7 ) 經濟部中央橾準扃負工消费合作社印製 得自固化聚酯醣解產物之改進加合物 #l(phr) 55.0 45.0、 1T line paper size is applicable to Chinese national rate (CNS &gt; Α4 wash grid (210Χ297mm &gt; I 27 _ A7 3υ5652 V. Description of invention (in)) Example 6 shows that the present invention improver adduct b is used in three The effectiveness of different low profile additives and amorphous unsaturated polyester resins in SMC formulations. Example 7 Multifunctional multi-components manufactured by glycolysis reaction between diethylene glycol and cured unsaturated resins Alcohol, which is capped with two to six high-oil fatty acid molecules and has various unsaturation levels of cis-butyrin. Reacts the cured polyester-styrene copolymer obtained from the sheet-shaped molding compound with diethylene glycol The excess ethylene glycol is stripped from the product to a hydroxyl value of about 505, meaning a hydroxyl equivalent of 111. Then it contains a 0.1% by weight Fascat 4100 catalyst (hydrated monobutyltin oxide from M &amp; T Chemicals) One equivalent of ethylene glycol and one equivalent of high oil fatty acid are combined in the reaction bottle. The mixed solution is reacted for about 6.5 hours at 1901-2101. The final acid value is 4.6. This product is named adduct GP-1. GP-2 is based on hydroxyl value 399 (equivalent weight 141 ) Is prepared by stripping the glycolysis product. One equivalent of this polyol and 2/3 equivalent of high oil fatty acid (equivalent weight of 286), 1/3 equivalent of maleic dioxane and dicyclopentadiene The reaction product (equivalent weight: 260) (then isomerized to fumaric acid isomer), and 0.1% by weight of Fascat 4100 were charged into the reaction bottle. The mixed solution was reacted at 19 ℃ -21 ℃ The final acid value is 2-3 hours. The adducts GP_3 and GP_4 are prepared by stripping the pyrolysis products based on base value 399 (equivalent weight 141). When one equivalent of this multicomponent monarch is equivalent to 2/3 equivalent weight High oil fatty acid (equivalent weight 286) and 0.1% by weight of Fascat ^ ⑼ in 丨 ⑽ ^ -19 (TC reaction for 3.5 hours, the final acid value is 2. Its semi-product is set aside and named GP-3. , Containing about 1/6 molar equivalent of hydroxy compound, reacted with 1/6 molar maleic butadiene liver at 12 ° C-U (rc for 25 hours. When infrared analysis of the product showed no residual maleic anhydride , The reaction is terminated. -28- * The paper size is applicable to the Chinese National Standard (CNS). M specifications (210X2 * ^ male seam) n ^ imm · ί ί 1 ^ 1 ^ in m ml m 1J, \ έ (please first Read the note on the back Please fill in this page again) A7 j, B7 printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (&gt; 7) The self-curing polyester glycolysis product printed by the Central Ministry of Economic Affairs Consumer Cooperative Improved adduct #l (phr) 55.0 45.0

實例7 成分 AROPOL Q6585 1 Ural loy 雜化樹 脂2035 LPA 苯乙歸 h合物GP-1 加合物GP-2 加合物GP-3 加合物GP_4 VDI钴加速劑 丁基m基甲苯 (抑制劑) 過氧化物引發劑 CaCO 3填充劑 硬脂酸鋅 (鑄膜釋放劑)Example 7 Ingredients AROPOL Q6585 1 Ural loy hybrid resin 2035 LPA styrene compound Hg GP-1 adduct GP-2 adduct GP-3 adduct GP_4 VDI cobalt accelerator butyl m-toluene (inhibitor ) Peroxide initiator CaCO 3 filler zinc stearate (cast film release agent)

MgO增稠劑 (33%分散體) Ashland 指數 GLORIA®) ⑧L0RIA爲Ashland Oil, Uc·的註册商標 1得自丙二醇和順丁烯二酸之非晶型不飽和聚g旨樹脂( 酸價28至32,於苯乙烯中不揮發物65%) ---I----- 坤衣------訂 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) Λ4現格(2丨0x297公錄) -2岔· 3υ5ΰ〇2 五、發明説明(28 ) 實例7中調配物#2和#4顯示加合物在URALLOY®2035低 廓形添加劑中之有效性。調配物#3示出將三分之一的高油 脂肪酸以具高度反應性之不飽和反丁烯二酸低聚物取代, 類著地降低改進劑加合物之有效性。另一方面,調配物#5 ,也含有不飽和部份。然而,順丁烯二酸之雙鍵與苯乙烯 的反應很慢,因此不會降低加合物GP-4乏有效性。 實例8説明酵酸樹脂作爲改進劑用之有效性。酵酸樹脂 基本上爲以脂肪酸爲末端之飽和聚酯。有關醇酸樹脂及其 技術之钦述,參考T.C.Patton之Alkyd Resin Technology, Interscience Publishers, 1962,或Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., vol. 2,p53ff 〇 酵酸樹脂之製備如下。將高油脂肪酸(570克)、異戊四 醇(190克)、和鉍酸(240克)裝填於兩升樹脂釜中,於400卞 加熱和攪拌1 1/2小時。除去約43毫升水,然後將釜溫增 加到480V,維持1小時。生成的酵酸AV爲3.4。冷卻至 150卞,將429克苯乙烯和0.3克對苯醌攪拌入樹脂中至產 生褐色溶液止。此溶液於下面使用,即组成物A中之醇酸 樹脂溶液。 下列調配物係舲27%重量比Γ短切0CF 980玻璃織維摻 和入SMC片中以測定以醉酸爲表面品質改進劑之有效性。 声達到適當模製黏度(約15-25百萬厘泊)後,於300卞和 1000psi模製2分鐘,使成爲大約100密耳厚之12吋X 12叶 面板。然後使用Lor ia表面分析儀評定這些面板的表面品 質。表中之數値爲Ashland指數値,數値愈低表示表面品 質愈佳。 -30- 本紙張尺度適用中國國家橾隼(CNS &gt; A4規格(2丨0X297公釐〉 ---------燊-- (請先閲讀背面之注意事項再填寫本頁) -* 經濟部中央揉準局員工消費合作社印製 Μ Β7 經濟部中央標準局員工消費合作社印製 五、發明説明(29 ) 實例8 調配物A 調配物B 不飽和衆醋 769g 720g LPA2 334 480 醇酸樹脂溶液 69 « 加速劑3 0.6 1.2 BHT4 6.0 12 苯乙烯 60 - 過苯甲酸第三丁醏 18 18 硬脂酸鋅 54 54 Ca(C03 ) 2640 2564 B-面5 42 32 L0RIA6 57 80 由上面實例8可見,组成物A(本發明之實例)與不含本 發明改進劑之組成物B相較下,顯著地具有較佳之表面品 質,縱使實例A中使用實際上較少的LPA(通常產生較差的 表面品質),仍見增進之表面。 1不飽和聚酯(以丙二醇和順丁烯二酐製備,使用6-8% 過量之二醇)之65%苯乙烯溶液(AV= 30) 2 Uralloy 85-05雜化樹脂,飽和聚酷/胺S旨LPA之40% 固形物苯乙烯溶液 -31- 本紙張尺度適用中國國家標率(CNS ) A4規格(210X297公釐) --------餐------ΪΤ------外 (讀先閱讀背面之注意事項再填寫本頁) 305632 A7 B7 五、發明説明(30 ) 3钴-有機酸鹽,12%金屬 4 丁基化m基甲苯(BHT)於苯乙烯中之10%溶液 5於低MW、低AV PG/順丁烯二酸聚酯中之33% MgO分 散體 6如LORIA表面分析儀所測定 ---------------訂 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央樣準局員工消費合作社印裝 —32 — 本紙張尺度適用中國國家樣隼(CNS ) A4規格(210X29*7公釐) A7 B7 五、發明説明(3l ) 實例9闡明於含有不飽和聚醏基底樹脂、反應性單體和 AROPOL Z8000低廓形添加劑之SMC調配物中改進劑加合物B 之使用。含有加合物B之調配物顯示增進之表面品質( Ashland指數)物理性質和水吸收性(ASTM D 570)。 ---------------訂 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消f合作社印製 -33- 本紙張尺度適用中國國家揉牟(CNS ) ( 210X297公釐) A7 B7 五、發明説明(32) 實例9 成分 調配物1 調配物2 調配物3 AR0P0L Q6585 1 67.5 75.0 75.0 AR0P0L Q8000 2 LPA(50%NV) 32.5 25.0 4 20.0 加合物B - - 4.0 苯乙烯 - - 1.0 丁基m基甲苯 0.1 0.1 0.1 過氧苯甲酸第三丁酯 1.5 1.5 1.5 填充劑 200.0 200.0 200.0 硬脂酸鋅 4.5 4.5 4.5 MgO增稠劑3 10.0 10.0 10.0 Ashland 指數 (表面品質) 73 94 66 抗張強度(ksi) 13.29 14.29 15.08 抗弩強度(ksi) 34,96 31.61 33.68 24小時水吸收性 (重量%) 0.77 0.68 0.42 I 訂 I&quot;- (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印聚 1非晶型UPE樹脂(丙二醇/順丁烯二酸),酸償28-32, 於苯乙稀中 65%NV,得自 Ashland Chemical Company 2飽和PE低廓形添加劑,於苯乙烯中50% NV,得自 Ashland Chemical Company 3 MgO於低酸價UPE中之11%分散體 本紙張尺度適用中國國家標準(CNS ) A4規格(_210X297公釐) A7 _____B7 五、發明説明(33 ) 實例10提供Budd Company美國專利4,622,354相位-穩 定劑的表現之説明。比較兩個製劑的紅外線光譜以決定長 鏈酸和聚醋多元酵的混合物是否在原位置反應。比較混合 物的紅外線光譜與酸和衆酯多元醇的反應產物之紅外線光 譜。 實例10 . 於混合1、6和10天後,聚醋多元醇及油酸和硬脂酸未反 應混合物之IR先譜示出與多元醇鲽基和酸基相同之羥基峰 。於混合1、6和10天後,混合物也示出與酸基和酯基相同 之重疊羰基峰。因此,沒有於原位置形成之多封端低衆物 加合物。如果於原位置發生反應,-0H和〉C=0峰之組態將 會由於去除羥基和酸基形成酯而改變。 比較反應的聚酯多元醇及油酸和硬脂酸之IR光譜與未反 應成分的IR光譜顯示,由於發生反應,-0H峰消失。重疊 -C00H和〉C=0峰之-C00H部份也消失,留下單一S旨黢基尖 峰〇 實例11報導使用酸混合物,未封端低聚物、酸與低衆物 之混合物、及封端低聚物加合物A之結果。美國卑利 4,622,354中分别使用脂肪酸或衆醏多元醇。 ^ n - I I I I - ------訂 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央榡準局員工消費合作社印製 適 尺 張 紙 -本 準 棣 一·家 A7 B7 經濟部中央標準局員工消費合作社印裝 3U5652 調釔物: 成分 #l(phr) #2(phr) #3(phr) #4(phr) #5(phr) AR0P0L 6585 1 65.5 65.5 65.5 65.5 65.5 URALL0Y 2035 2 30.0 30.0 30.0 30.0 30.0 苯乙稀 4.5 0 0 0 0 油酸 0 2.3 0 1.1 0 硬脂酸 0 2.3 0 1.1 0 加合物Α之未 封端低聚物 0 0 4.5 2.3 0 加合物A 0 0 0 0 4.5 環己烷甲酸鈷 (12%鈷金屬) 0.1 0.1 0.1 0.1 0.1 第三丁基m基 甲苯 0.1 0.1 0.1 0.1 0.1 硬脂酸鋅 4.5 4.5 4.5 4.5 4.5 碳酸鈣填充劑 200.0 200.0 200.0 200.0 200.0 過氧苯甲酸 第三丁醏 1.5 1.5 1.5 1.5 1.5 MgO增稠劑3 3.5 3.5 3.5 3.5 3.5 -36-MgO thickener (33% dispersion) Ashland Index GLORIA®) ⑧L0RIA is a registered trademark of Ashland Oil, Uc. 1 Amorphous unsaturated polyg resin obtained from propylene glycol and maleic acid (acid value 28 to 32, 65% of non-volatile matter in styrene) --- I ----- Kunyi ------ ordered (please read the precautions on the back before filling this page) This paper size is applicable to Chinese national standards (CNS) Λ4 present case (2 丨 0x297 public record) -2 Cha · 3υ5ΰ〇2 V. Description of the invention (28) The formulations # 2 and # 4 in Example 7 show the adduct in URALLOY® 2035 low profile additive The effectiveness. Formulation # 3 shows that replacing one-third of the high oil fatty acids with highly reactive unsaturated fumaric acid oligomers significantly reduces the effectiveness of the modifier adduct. On the other hand, formulation # 5 also contains unsaturated parts. However, the double bond of maleic acid reacts slowly with styrene, so it does not reduce the effectiveness of the adduct GP-4. Example 8 illustrates the effectiveness of fermented acid resin as an improver. Fermented acid resin is basically a saturated polyester with fatty acid as the end. For a description of alkyd resin and its technology, refer to Alkyd Resin Technology, Interscience Publishers, 1962 of T.C. Patton, or Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., Vol. 2, p53ff 〇 The preparation of fermented acid resin is as follows. A two-liter resin kettle was charged with high-oil fatty acid (570 g), isopentaerythritol (190 g), and bismuth acid (240 g), and heated and stirred at 400 Bian for 1 1/2 hours. After removing about 43 ml of water, the kettle temperature was increased to 480V for 1 hour. The AV produced was 3.4. After cooling to 150 ° C, 429 g of styrene and 0.3 g of p-benzoquinone were stirred into the resin until a brown solution was produced. This solution is used in the following, namely the alkyd resin solution in composition A. The following formulation was prepared by blending 27% by weight of Γ chopped 0CF 980 glass fabric into SMC tablets to determine the effectiveness of using drunk acid as a surface quality improver. After the sound has reached the proper molding viscosity (about 15-25 million centipoise), it is molded at 300 Bian and 1000 psi for 2 minutes to make it into a 12-inch X 12-blade panel approximately 100 mils thick. The surface quality of these panels was then evaluated using a Lor ia surface analyzer. The numerical values in the table are Ashland index values. The lower the numerical value, the better the surface quality. -30- This paper scale is applicable to the Chinese National Falcon (CNS & A4 specifications (2 丨 0X297mm> --------- 燊-(please read the precautions on the back and fill in this page)- * Printed by the Employee Consumer Cooperative of the Central Ministry of Economic Affairs of the Ministry of Economic Affairs Μ Β7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of Invention (29) Example 8 Formulation A Formulation B Unsaturated Public Vinegar 769g 720g LPA2 334 480 Alkyd Resin solution 69 «Accelerator 3 0.6 1.2 BHT4 6.0 12 Styrene 60-tertiary butyl perbenzoate 18 18 Zinc stearate 54 54 Ca (C03) 2640 2564 B-side 5 42 32 L0RIA6 57 80 Example 8 from above It can be seen that the composition A (an example of the present invention) has significantly better surface quality compared to the composition B without the modifier of the present invention, even though actually less LPA is used in the example A (generally producing poorer Surface quality), still see the surface of improvement. 1 unsaturated polyester (prepared with propylene glycol and maleic anhydride, using 6-8% excess glycol) in 65% styrene solution (AV = 30) 2 Uralloy 85 -05Hybrid resin, 40% of solid polystyrene / amine S purpose LPA, styrene soluble -31- This paper scale is applicable to China National Standard Rate (CNS) A4 specification (210X297mm) -------- Meal ------ ΪΤ ------ Outside (Read first (Notes to fill out this page) 305632 A7 B7 5. Description of the invention (30) 3 Cobalt-organic acid salt, 12% metal 4 10% solution of butylated m-toluene (BHT) in styrene 5 at low MW, 33% MgO dispersion 6 in low AV PG / maleic acid polyester as determined by LORIA surface analyzer --------------- (please read the notes on the back first (Fill in this page again) Printed by the Employees ’Consumer Cooperative of the Central Prototype Bureau of the Ministry of Economic Affairs — 32 — This paper size applies to the Chinese National Falcon (CNS) A4 specification (210X29 * 7mm) A7 B7 V. Invention description (3l) Example 9 Clarified the use of improver adduct B in SMC formulations containing unsaturated polyamide base resins, reactive monomers and AROPOL Z8000 low profile additives. The formulations containing adduct B show improved surface quality (Ashland Index) Physical properties and water absorption (ASTM D 570). --------------- Order (please read the notes on the back before filling this page) Member of the Central Standards Bureau of the Ministry of Economic Affairs Printed by Gongxiao F Cooperative Society-33- This paper scale is applicable to China National Crushing Mouth (CNS) (210X297mm) A7 B7 V. Description of Invention (32) Example 9 Ingredient Blend 1 Blend 2 Blend 3 AR0P0L Q6585 1 67.5 75.0 75.0 AR0P0L Q8000 2 LPA (50% NV) 32.5 25.0 4 20.0 Adduct B--4.0 Styrene--1.0 Butyl m-toluene 0.1 0.1 0.1 Third butyl peroxybenzoate 1.5 1.5 1.5 Filler 200.0 200.0 200.0 Zinc stearate 4.5 4.5 4.5 MgO thickener 3 10.0 10.0 10.0 Ashland index (surface quality) 73 94 66 Tensile strength (ksi) 13.29 14.29 15.08 Crossbow strength (ksi) 34,96 31.61 33.68 24-hour water absorption (Wt%) 0.77 0.68 0.42 I order I &quot;-(please read the precautions on the back before filling in this page) Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperatives printed poly 1 amorphous UPE resin (propylene glycol / maleic acid) , Acid compensation 28-32, 65% NV in styrene, obtained from Ashland Chemical Company 2 saturated PE low profile additive, 50% NV in styrene, from Ashland Chemical Company 3 MgO in low acid value UPE Of the 11% dispersion of this paper is suitable China National Standard (CNS) A4 size (_210X297 mm) A7 _____B7 V. Description of the Invention (33) provided Example 10 in U.S. Patent 4,622,354 Budd Company phase - description of the performance of the stabilizer. The infrared spectra of the two preparations were compared to determine whether the mixture of long-chain acid and polyacrylic acid multi-enzyme reacted in situ. Compare the infrared spectrum of the mixture with the infrared spectrum of the reaction product of the acid and the ester polyol. Example 10. After 1, 6 and 10 days of mixing, the IR spectrum of the unreacted mixture of the vinegar polyol and oleic acid and stearic acid showed the same hydroxyl peak as the polyhydric plaque and acid groups. After 1, 6, and 10 days of mixing, the mixture also showed the same overlapping carbonyl peak as the acid group and the ester group. Therefore, there are not many blocked adducts formed in situ. If the reaction occurs at the original position, the configuration of -0H and> C = 0 peaks will change due to the removal of hydroxyl groups and acid groups to form esters. Comparing the IR spectrum of the reacted polyester polyol and oleic acid and stearic acid with the IR spectrum of the unreacted component shows that the -0H peak disappears due to the reaction. Overlapping -C00H and> C = 0 peaks -C00H part also disappeared, leaving a single S-based peak. Example 11 reports the use of acid mixtures, unblocked oligomers, a mixture of acid and low congregation, and blocked The result of oligomer adduct A. Fatty Acid or Zhongli Polyols are used in U.S. Pelican 4,622,354, respectively. ^ n-IIII------- Order (please read the precautions on the back before filling in this page) Printed a suitable size sheet of paper by the Consumer Cooperative of the Central Bureau of Economics of the Ministry of Economic Affairs-This standard is A1 B7 Economy 3U5652 Yttrium adjustment printed by the Ministry of Standards and Staff Consumer Cooperative: Ingredient #l (phr) # 2 (phr) # 3 (phr) # 4 (phr) # 5 (phr) AR0P0L 6585 1 65.5 65.5 65.5 65.5 65.5 URALL0Y 2035 2 30.0 30.0 30.0 30.0 30.0 Styrene 4.5 0 0 0 0 Oleic acid 0 2.3 0 1.1 0 Stearic acid 0 2.3 0 1.1 0 Unblocked oligomer of adduct A 0 0 4.5 2.3 0 Adduct A 0 0 0 0 4.5 Cobalt cyclohexanecarboxylate (12% cobalt metal) 0.1 0.1 0.1 0.1 0.1 Third butyl m-toluene 0.1 0.1 0.1 0.1 0.1 Zinc stearate 4.5 4.5 4.5 4.5 4.5 Calcium carbonate filler 200.0 200.0 200.0 200.0 200.0 Peroxybenzoic acid tertiary butyl chloride 1.5 1.5 1.5 1.5 1.5 MgO thickener 3 3.5 3.5 3.5 3.5 3.5 3.5 -36-

五、發明説明(34 ) 實例U5. Description of the invention (34) Example U

酸、低衆物、封端低聚物加合物A矣A 添加劑(phr) ASHLAND INDEX 對照組 #1 81 油酸/硬脂酸(4.5)[50/50] #2 71 加合物4之?£170£6低衆物(4.5)#3 78 低衆物/混合酸(4.5)[50Λ01 #4 69 封端低聚物加合物Α(4.5) #5 60* 本紙張尺度適用中國國家榡‘(CNS ) Α4規格(2丨0X297公釐) 經濟部中央標準局員工消費合作社印製 kl B7 五、發明説明(35 ) 1非晶型不飽和聚酯樹脂(丙二醇和順丁烯二酸),酸價 28至32,於苯乙烯中不揮發物65%,得自Ashland Chemical Company 2鉋和聚酯/胺S旨低廓形添加劑,於苯乙烯中40% NV, 得自 Ashland Chemical Company * 3 MgO於低酸價UPE不飽和聚酯載體中之11%分散體 —37 - 本紙張尺度適用中國國家標隼(CNS ) A4規格(210X297公釐〉 —^1- —^1— I —^1— fn (m -- 1-—- I In ^1^1.--aJ (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明説明(36 ) 回顧實例11顯示使用本發明之封端低聚物加合物表面品 質改進劑,得到優越的表面品質。Ashland指數60爲特A 級汽車零件品質。 下面實例12説明以環狀酸將聚酯低聚物封端以形成本發 明之多封端低聚物加合物表面品質改進劑之用途。 I 1 訂 故 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消f合作社印裝 -38- 本紙張尺度適用中國國家標準_( CNS ) A4規格(210X297公釐) 五、發明説明(37 ) A7 B7 實例12 以松脂(樹脂酸)封端之表面品質低衆物加合物 製備: 填裝: 成分 克 己二酸/二乙二醇 聚酯低聚物 〔0H〕値=131.5 〔AV〕=1.3 441.4 松脂 〔AV〕=168 320 Fascat 4100 單水合之丁基氧化踢催 化劑Μ &amp; T Chemicals 之產品 0.38 1 111— ^—.^1 —^^1· —^1 - - - - - - - I 1^1 --- 11—--SJ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央棟準局員工消費合作社印製 將各成分裝塡於卜升樹脂釜中,混合時以氮稍加沖洗並 加熱至約2401〇。形成醏時將水去除。反應繼績進行至酸 價(毫克/克試樣)降低至钓7.6爲止。將產物溶於以100??111 第三丁基-兒茶酚抑制之苯乙烯中至達80%不揮發物。 -39- 本紙張尺度適用中國國家標车(CNS ) A4規格(210X297公釐) 3U5852 五、發明説明(38) 松脂酸添加劑有效性試驗 成分 對照组 w/添加劑 (phr) (phr) AROPOL Q6585 1 72.0 72.2 LPA’Uralloy LP20202 21.2 21.2 苯乙烯 6.8. 3.2 松脂封端之加合物 0 3.2 環己垸甲酸鈷(12%鈷金屬) 0.1 0.1 第三丁基m基甲苯(引發劑) 0.1 0.1 過氧苯甲酸第三丁醏(引發劑) 1.5 1.5 碳酸鈣填充劑 200.0 200.0 MgO增稠劑3 3.5 3.5 Ashland 指數 1〇〇 83 回顧實例12顯示,環狀末端基固可用於輿衆酯多元醇反 應以形成有效之多封端低衆物和合物表面品質改進劑。 策 n 訂 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 1非晶型不餘和衆齒樹脂(丙二酵和順丁稀二酸),酸償 28至32,於苯乙烯中不揮發物65%,得自AshlandAdditives of acids, low public goods, blocked oligomers A 焣 A Additive (phr) ASHLAND INDEX Control group # 1 81 Oleic acid / stearic acid (4.5) [50/50] # 2 71 adduct 4 of ? £ 170 £ 6 Low public substance (4.5) # 3 78 Low public substance / mixed acid (4.5) [50Λ01 # 4 69 End-capped oligomer adduct Α (4.5) # 5 60 * This paper size is suitable for Chinese national '(CNS) Α4 specifications (2 丨 0X297mm) Kl B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (35) 1 Amorphous unsaturated polyester resin (propylene glycol and maleic acid) , Acid value 28 to 32, 65% non-volatile in styrene, obtained from Ashland Chemical Company 2 planer and polyester / amine S low profile additives, 40% NV in styrene, obtained from Ashland Chemical Company * 3 11% dispersion of MgO in UPE unsaturated polyester carrier with low acid value -37-This paper scale is applicable to China National Standard Falcon (CNS) A4 specification (210X297mm) — ^ 1- — ^ 1—I — ^ 1— fn (m-1 -—- I In ^ 1 ^ 1 .-- aJ (please read the precautions on the back before filling in this page) A7 B7 5. Description of the invention (36) Review example 11 shows the use of the invention The surface quality improver of the end-capped oligomer adduct obtains excellent surface quality. Ashland index 60 is the quality of special A-level automotive parts. Example 12 below illustrates the ring shape The use of acid to block the polyester oligomer to form the surface quality improver of the multi-blocked oligomer adduct of the present invention. I 1 Ordered (please read the precautions on the back before filling this page) Central Ministry of Economic Affairs Printed by the Bureau of Standards and Social Welfare Cooperative Society-38- This paper scale is applicable to the Chinese National Standard _ (CNS) A4 Specification (210X297 mm) V. Description of the Invention (37) A7 B7 Example 12 Surface blocked with rosin (resin acid) Preparation of adducts of low quality public materials: Filling: Ingredients adipic acid / diethylene glycol polyester oligomer 〔0H〕 value = 131.5 〔AV〕 = 1.3 441.4 rosin 〔AV〕 = 168 320 Fascat 4100 monohydrate Butyl oxidation kick catalyst Μ &amp; T Chemicals product 0.38 1 111— ^ —. ^ 1 — ^^ 1 · — ^ 1-------I 1 ^ 1 --- 11 ---- SJ (please Read the precautions on the back and then fill out this page) Printed by the Employee Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs. Pack the ingredients in a Busheng resin kettle, rinse with nitrogen and heat to about 2401. The water was removed at the time. The reaction continued until the acid value (mg / g sample) decreased to 7.6. Was dissolved in tert-butyl 100 ?? 111 - suppression of catechol in styrene to 80% nonvolatiles. -39- This paper scale is applicable to China National Standard Vehicle (CNS) A4 specification (210X297mm) 3U5852 V. Description of invention (38) Effectiveness test component of rosin acid additives w / additive (phr) (phr) AROPOL Q6585 1 72.0 72.2 LPA'Uralloy LP20202 21.2 21.2 Styrene 6.8. 3.2 Rosin-terminated adduct 0 3.2 Cobalt cyclohexyl formate (12% cobalt metal) 0.1 0.1 Third butyl m-toluene (initiator) 0.1 0.1 Peroxygen Tertiary butyl benzoate (initiator) 1.5 1.5 Calcium carbonate filler 200.0 200.0 MgO thickener 3 3.5 3.5 Ashland index 10083 Review example 12 shows that cyclic end group solids can be used in the reaction of public ester polyols to Forms an effective surface quality improver for many end-capped low-end compounds. Policy n order (please read the precautions on the back before filling in this page) Printed by the Ministry of Economic Affairs, Central Standards Bureau, Employee Consumer Cooperatives, 1 amorphous and all-tooth resin (malonase and maleic acid), acid compensation 28 to 32, 65% non-volatile in styrene, from Ashland

Chemical Company 2飽和衆酯/胺酯低廓形添加劑,於苯乙烯中50%NV, 得自 Ashland Chemical Compay 3於低酸償不飽和衆酯載體中之33% M&amp;0分散體 —40 — 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中央標隼局員工消費合作社印製 A7 B7 _____ _— 五、發明说明(的) 窒溫之模製 欲從熱固樹脂模製得到平滑、表面形成良好之零件固 化期間收缩性控制得好是很重要的。模製係於室溫或升高 之溫度下進行則無關緊要。有史以來一直使用熱塑性低廓 形添加劑來控制不飽和聚醏樹脂之固化收縮性。不幸地, 迻些低廓形添加劑的加入時常減緩及/或降低樹脂系固化 的程度。因此,低含量的低廓形添加劑較爲有利。實例13 所示之調配物説明於室溫固化系使用加合物B之優點。 -------- 梦------訂 一請先S讀背面之注意事項再填寫本I!) 實例13 成分 (phr) (phr) AROPOL Q6585 1 34.9 30.0 AROPOL 8014 2 11.6 10.0 AROPOL 2036 3 15.0 23.0 LPA,URALL0Y LP2020 4 10.0 7.0 LPA,URALL〇Y Q80005 10.0 7.0 加合物B 0 4.0 苯乙烯 8.9 12.5 甲基丙歸酸肀8¾單體 4.0 4.0 發煙矽石 0 0.7 Tween 20界面活性劑 0 0.2 四氫醌 0.2 0.04 十氫蒌酸鈷(12%金屬钴) 0.4 0.4 二甲基笨胺 0.2 0.2 辛酸鉀(15%鉀) 0.2 0.1 二曱基對甲苯胺 0.1 0.05 LuPers〇l DDM9 2.0 1.25 本紙張认適财國國家標準(CNS) A4規格(2iqx297公釐)_41_ A 7 B7 五、發明説明(4〇 ) 周圍杯凝膠(cup gel) 之最高溫度 表現: 杯凝膠 固化 零件外觀 340T(170eC) 362^(183-〇) 杯凝膠樹脂看杯凝膠樹脂看 得見的收縮 得見的膨脹 固化不良·良好,硬固化 零件上有玻 零件表面平滑 璃印 有光澤 經濟部争央搮準局員工消費合作杜印裝 1非晶型不飽和聚酯樹脂(丙二醇和順丁烯二酸),酸償 28至32,於苯乙烯中不揮發物65%,得自Ashland Chemical Company 2於苯乙烯中不揮發物72-75%,酸償18-35,史托克黏 度10-12 3不飽和聚酯基底樹脂,得自58/42/80/20莫耳%之順 丁稀二肝/異S太酸/二乙二酵/乙二醇 4飽和聚醏/胺酯低廓形添加劑’於苯乙烯中不揮發物 50%,得自 Ashland Chemical Compay 5飽和聚δ旨低廓形添加劑,不揮發物50%,Ashland Chemical Compay phr=每100份樹脂之份數,其中樹脂典型地包括不飽和 (反應性)樹脂、飽和樹脂、和反應性單體。 -42- 本紙張尺度適用中國國家標準(CNS ) A4规格(21〇Χ297公着) (請先閲讀背面之注意事項再填寫本頁) 丁 A7 B7 505852 五、‘發明説明(41 ) 實例13之模製於室溫在未經加熱的鑄模中進行,而實例 1-5中,晶型樹脂基底系統係於194°F(90eC)模製,實例 6-9、11和12之系統係於300卞(1501〇)模製。 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印聚 -43- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)Chemical Company 2 saturated urethane / urethane low profile additive, 50% NV in styrene, from 33% M &amp; 0 dispersion of Ashland Chemical Compay 3 in a low acid unsaturated urethane carrier—40—present The paper standard is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm). The A7 B7 is printed by the Employees ’Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs. _____ _— V. Description of the invention It is important to produce smooth, well-formed parts with good shrinkage control during curing. It does not matter if the molding is performed at room temperature or elevated temperature. Historically, thermoplastic low-profile additives have been used to control the curing shrinkage of unsaturated polyimide resins. Unfortunately, the addition of low profile additives often slows and / or reduces the degree of curing of the resin system. Therefore, low levels of low profile additives are more advantageous. The formulation shown in Example 13 illustrates the advantages of using Adduct B for curing at room temperature. -------- Dream ------ If you order one, please read the precautions on the back before filling in this I!) Example 13 Composition (phr) (phr) AROPOL Q6585 1 34.9 30.0 AROPOL 8014 2 11.6 10.0 AROPOL 2036 3 15.0 23.0 LPA, URALL0Y LP2020 4 10.0 7.0 LPA, URALL〇Y Q80005 10.0 7.0 Adduct B 0 4.0 Styrene 8.9 12.5 Methylpropionic acid monomer 8¾ monomer 4.0 4.0 Fuming silica 0 0.7 Tween 20 interface Active agent 0 0.2 Tetrahydroquinone 0.2 0.04 Cobalt decahydroentanoate (12% metallic cobalt) 0.4 0.4 Dimethylbenzylamine 0.2 0.2 Potassium octoate (15% potassium) 0.2 0.1 Dimethyl p-toluidine 0.1 0.05 LuPers〇l DDM9 2.0 1.25 This paper conforms to the national standard (CNS) A4 specification (2iqx297 mm) of the financial country _41_ A 7 B7 5. Description of the invention (4〇) The highest temperature performance of the surrounding cup gel: cup gel cured parts Appearance 340T (170eC) 362 ^ (183-〇) Cup gel resin, see the cup gel resin, the shrinkage can be seen, the swelling and curing is not good Controversial Bureau of Consumer Affairs and Consumer Cooperation Du Printing 1 Amorphous Unsaturated Polyester Resin ( Glycol and maleic acid), acid compensation 28 to 32, 65% non-volatile matter in styrene, obtained from Ashland Chemical Company 2 non-volatile matter in styrene 72-75%, acid compensation 18-35, history Torque viscosity 10-12 3 unsaturated polyester base resin, obtained from 58/42/80/20 mol% cis-butadiene diisopropanol / isosporic acid / diethylene glycol / glycol 4-saturated polyimide / Urethane low profile additives' 50% nonvolatiles in styrene, obtained from Ashland Chemical Compay 5 saturated poly delta low profile additives, nonvolatiles 50%, Ashland Chemical Compay phr = parts per 100 parts resin The number of resins typically includes unsaturated (reactive) resins, saturated resins, and reactive monomers. -42- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (21〇Χ297 public) (please read the precautions on the back and then fill out this page) Ding A7 B7 505852 Five, 'invention description (41) Example 13 of Molding was performed at room temperature in an unheated mold, while in Examples 1-5, the crystalline resin substrate system was molded at 194 ° F (90eC), and the systems of Examples 6-9, 11 and 12 were at 300 Bian (1501〇) is molded. (Please read the precautions on the back before filling out this page) Printed Poly-Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -43-

Claims (1)

ABCD ~2---~-_ 六、申請專利範圍 專利申請案第83110邮3號 ROC Patent Appln. No. 83110653 修正之申請專利範圍中文本-附件一 Amended Claims in Chinese - Enel. I &quot; 國86年2月μ曰送呈) (Sumitted on February I 少,1997) L一種樹脂組成物,供進一步地反應以形成固化熱固模 製用品,包括: (a) —不飽和聚g旨, (b) —熱塑性低廓形添加劑,用於增進所述模製用品 之表面品質,係選自飽和衆酯、聚膝基甲酸酯、 聚甲基丙烯酸甲醋、聚乙酸乙烯醏、飽和聚醋胺 基甲酸乙酯或其混合物,及 (c) 與不飽和聚酷共聚合之一或多種燁煙不飽和單體 y 其特徵係在於更進一步包括 1至4份(每百份樹脂)之⑷一多封端(pi〇ycapped)低 聚物加合物’其增進成分(b)之表現,且與固化之不 飽和衆酯和單體不相容’所述多封端低聚物加合物係 選自於高油脂肪酸與聚酷多元醇之物、硬脂脂肪 酸與雙吩A和環氧乙烷或環氧丙垸之產物的加合物、 高油脂肪酸和雙環氧化物樹脂的B羥基喃、松脂酸多 封端低聚物加合物或其混合物。S • 44 - 本紙張尺度適用中國國家標準(CNS ) Λ4規格(210X297公釐) I I - Ϊ ...... - me -I .11 · I ! - n^— I—. I 1^1 II-、〆OJml - - - I (請先閱讀背而之注意事項再填寫本頁) 經濟部中央標率局員工消費合作社印製 ABCD 〇u5652 六、申請專利範圍 2. 根據申請專利範圍第1項之組成物,其中所述聚S旨多 元醇係利用二乙二醇將聚對酞酸乙二醏醣解而形成。 3. 根據申請專利範圍第1項之組成物,其中所述不飽和 聚酯爲結晶,所述晶型聚S旨於25°C及50%以上之苯乙 烯溶液中爲固體。 4. 根據申請專利範圍第1項之組成物,其中所述不飽和 聚酯爲非晶型。 5. 根據申請專利範圍第1項之組成物,其中所述不飽和 聚S旨由晶型聚酯和非晶型聚酯的混合物所組成。 6. 根據申請專利範圍第1項之組成物,其中(d)係爲高油 酸與平均分子量値低於800之聚S旨多元醇的加合物。 7. 根據申請專利範圍第1項之組成物,其中所述聚酯多 元醇係將己二酸與二乙二醇反應而製得者。 m mfl —^ϋ n^i In— Km illflf I ml ^^^^1 me m 一 ’ (請先閱讀背而之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標隼(CNS ) A4規格(210Χ2ί»7公嫠)ABCD ~ 2 --- ~ -_ VI. Application for Patent Scope Patent Application No. 83110 Post No. 3 ROC Patent Appln. No. 83110653 Amended Claims in Chinese-Annex I Amended Claims in Chinese-Enel. I &quot; Country (Feed in February, 86) (Sumitted on February I, 1997) L A resin composition for further reaction to form a cured thermoset molding product, including: (a) —Unsaturated polyg purpose, (b )-Thermoplastic low profile additive, used to improve the surface quality of the molded article, is selected from the group consisting of saturated urethane, polymethyl urethane, polymethyl methacrylate, polyvinyl acetate, and saturated polyamidoamine Ethyl urethane or a mixture thereof, and (c) copolymerized with unsaturated polyacrylic acid, one or more of ye fu unsaturated monomer y, characterized by further including 1 to 4 parts (per hundred parts of resin) ⑷ A multi-capped oligomer adduct 'improves the performance of component (b) and is incompatible with cured unsaturated esters and monomers' said multi-capped oligomer adduct It is selected from the group consisting of high-oil fatty acids and polyhydric polyols, stearic fatty acids and B-hydroxy-pyran A and ethylene oxide adduct or product glycidoxy embankment, the high oil fatty acid and diepoxide resin, more acid rosin adduct oligomer terminated, or mixtures thereof. S • 44-This paper scale applies the Chinese National Standard (CNS) Λ4 specification (210X297mm) II-Ϊ ......-me -I .11 · I!-N ^ — I—. I 1 ^ 1 II-, 〆OJml---I (please read the precautions before filling in this page) ABCD 〇u5652 printed by the Employee Consumer Cooperative of the Central Standard Rate Bureau of the Ministry of Economic Affairs 6. Scope of patent application 2. According to the scope of patent application No. 1 The composition of the above item, wherein the poly-S-polyol is formed by glycolysis of polyethylene terephthalate with diethylene glycol. 3. The composition according to item 1 of the patent application scope, wherein the unsaturated polyester is crystalline, and the crystalline poly S is intended to be solid in a styrene solution at 25 ° C and 50% or more. 4. The composition according to item 1 of the patent application scope, wherein the unsaturated polyester is amorphous. 5. The composition according to item 1 of the patent application scope, wherein the unsaturated poly-S is composed of a mixture of crystalline polyester and amorphous polyester. 6. The composition according to item 1 of the patent application scope, where (d) is an adduct of high oleic acid and a poly S-polyol having an average molecular weight of less than 800. 7. The composition according to item 1 of the patent application scope, wherein the polyester polyol is prepared by reacting adipic acid with diethylene glycol. m mfl — ^ ϋ n ^ i In— Km illflf I ml ^^^^ 1 me m one '(please read the precautions before filling this page) Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs printed this paper standard Applicable to China National Standard Falcon (CNS) A4 specification (210Χ2ί »7 Gongmai)
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Publication number Priority date Publication date Assignee Title
US5744816A (en) * 1996-09-04 1998-04-28 Premix, Inc. Low pressure sheet molding compounds
US6083312A (en) * 1997-03-27 2000-07-04 Basf Corporation Low VOC coatings
US5880180A (en) * 1997-09-26 1999-03-09 Ashland Inc. Aldimine surface quality enhancers
US6492462B2 (en) 1998-01-16 2002-12-10 Landec Corporation Side chain crystalline polymer as rheology modifier for crosslinked polymer
EP0930343A3 (en) 1998-01-16 2000-05-31 Landec Corporation Low profile additives for crosslink resins
US6900261B2 (en) * 2001-06-12 2005-05-31 The University Of Delaware Sheet molding compound resins from plant oils
US20060252869A1 (en) * 2005-05-09 2006-11-09 Ashland Inc. Synergistic filler compositions and low density sheet molding compounds therefrom
US20060249869A1 (en) * 2005-05-09 2006-11-09 Ashland Inc. Low-density, class a sheet molding compounds containing divinylbenzene
US20070173584A1 (en) * 2006-01-23 2007-07-26 Ashland Licensing And Intellectual Property Llc Composite polymers
US20080090954A1 (en) * 2006-10-17 2008-04-17 Ashland Licensing And Intellectual Property Llc Low shrinkage sheet molded composite formulations
US7985826B2 (en) 2006-12-22 2011-07-26 Reichhold, Inc. Molding resins using renewable resource component
US20090281230A1 (en) * 2008-05-09 2009-11-12 Ashland Licensing And Intellectual Property Llc Branched low profile additives and methods of production
US9034982B2 (en) 2009-08-12 2015-05-19 Ashland Licensing And Intellectual Property, Llc Formulations comprising isosorbide-modified unsaturated polyester resins and low profile additives which produce low shrinkage matrices
CA3235497A1 (en) * 2021-10-18 2023-04-27 Polynt Composites USA, Inc. Thermosetting compositions for additive manufacturing
WO2023154193A1 (en) * 2022-02-08 2023-08-17 Teijin Automotive Technologies, Inc. Sheet molding composition with limited degassing

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4555534A (en) * 1981-03-26 1985-11-26 Union Carbide Corporation Uniformly pigmented, low shrinking polyester molding compositions
US4622354A (en) * 1985-10-22 1986-11-11 The Budd Company Phase stabilized polyester molding material
NL8701932A (en) * 1987-08-18 1989-03-16 Dsm Resins Bv THERMO-HARDBAR COMPOSITION.
US5100935A (en) * 1990-07-19 1992-03-31 The Budd Company Flexible sheet molding compound and method of making the same

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